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Manual Physical Chemistry III Part 1 (Surface Chemistry) Part 2 (Catalysis) Part 3 (Colloids) Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Chemistry Department MANUAL PHYSICAL CHEMISTRY III Table of Contents Experimental 1: Determination of Surface Tension of Liquids by drop weight Method ............................................ 2 Experimental 2: Determination of Surface Tension Liquids by Capillary Rise Method ............................................... 8 Experimental 3: To find out the partition coefficient of iodine between carbon tetrachloride and water. ................ 17 Experimental 4: To find out the equilibrium constant for the tri-iodide formation .................................................. 17 Experimental 5: Determination of the Adsorption Parameters of Oxalic acid on Charcoal ..................................... 22 Experimental 6 Experimental 6: Adsorption of acetic acid on to activated charcoal .............................................. 27 Experimental 7: To find out the partition coefficient of iodine between carbon tetrachloride and water. ................ 31 Experimental 8: To find out the equilibrium constant for the tri-iodide formation .................................................. 37 Experimental 9: Determination of the Adsorption Parameters of Oxalic acid on Charcoal ..................................... 40 Experimental 10: To make a colloid and demonstrate its properties......................................................................... 43 Experimental 11: Stability of the emulsions ............................................................................................................ 51 Experimental 12: To find the critical point for colloidal mixtures composed of different types of starches. ........... 53 Experimental 13: Find out the formula of cupper ammonia complex ...................................................................... 57 Experimental 14: Surface tension of n-butanil solution ........................................................................................... 59 Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 1 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 1: Determination of Surface Tension of Liquids by drop weight Method The surface tension of liquids measured with the stalagmometer Surface tension of liquids The molecules of liquids attract each other by cohesive forces resulting into small distances between the molecules (on the order of 0.1 nm). Thus the compressibility of liquids is lower than that of gas, while the density is much higher. On the other hand, these cohesive forces are not strong enough to result into the fixed position of molecules that can be seen in solid matter. Liquids do not keep a fixed shape, but adapt the shape of a container. Attractive cohesive forces are short range forces which are based on the electronic interactions. They affect molecules in their close vicinity only (zone of molecular interaction). In the bulk of the liquid, each molecule is attracted equally in all directions by the neighboring molecules; hence zero net force (Fig. 1). However, the molecules at the surface do not have other like molecules on all sides around them and they are pulled inwards the liquid core by non-zero net force (Fig. 1). Consequently, they cohere more strongly to those associated with them directly on the surface and form a surface "film". Nevertheless, these surface molecules are in the energetically unfavorable state, which forces liquid to minimize the surface area. The geometrical requirement of smallest surface area at the fixed volume is satisfied by the sphere. It is the reason why the free drops of water form spherical droplets. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 2 Chemistry Department MANUAL PHYSICAL CHEMISTRY III The energetic definition of the surface tension (equation 1) is not the only way to describe it. We can derive it also from the simple experiment shown in Figure 2. It involves the wire rim with the AB side being able to move, and a soap film spanning the space inside the rim. We can observe that the movable wire AB is being pulled towards the soap film, as its area is shrinking down. There is a force in a plane of soap film acting in a direction perpendicular to the wire. It is called the surface force, and is expressed as Where l is the length of AB wire and is the surface tension. According to this, surface Tension is defined as a ratio of surface force to a length of rim that is pulled by this force Equation (4) defines the surface tension again in units of N/m. The measurement of the surface tension of liquids using the stalagmometer. Stalagmometer is a glass tube, widened in the middle part (Fig. 3). Its volume is calibrated by the scale shown on the tube, or by the top and bottom lines. The bottom part of stalagmometer is modified such that the liquid flowing through its smaller diameter forms the drops. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 3 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 4 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental procedure: 1. Mount the clean and dry stalagmometer on the vertical stand. 2. Weigh the mass of the weighing bottle m0. 3. Fill the beaker with distilled water. Mount the tubing with balloon on the top end of stalagmometer. Immerse the bottom end of stalagmometer into water and fill it up, such that the water level is above the wide part of stalagmometer. 4. Remove the balloon and collect 20 water drops into the weighing bottle. 5. Weigh the mass of the weighing bottle with water and determine the mass of 20 drops. 6. Empty the weighing bottle and stalagmometer, dry them and prepare for the next measurement. 7. Repeat steps 2-6 for liquids with the unknown surface tension. 8. Knowing the temperature in laboratory, determine the water surface tension using values from the table 1, and calculate the surface tensions of studied liquids according to the equation (7). Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 5 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental procedure: 1. Fill the stalagmometer up to the top mark with distilled water. Release water to the Weighing bottle and count how many drops it takes to decrease the water level in stalagmometer down to bottom mark. Write down the number of drops nH20. 2. Empty and dry the weighing bottle and stalagmometer, and prepare them for the next measurement. 3. Repeat steps 1 and 2 for liquids with the unknown surface tension. 4. Write down the densities of studied liquids according to the notes on bottles, and density of distilled water at the actual temperature in laboratory from the table 1. Using equation (10), calculate the surface tension for all the studied liquids. 5. Compare results obtained via the drop-weight method and drop counting method. Tab. 1: The temperature dependence of the surface tension and distilled water density. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 6 Chemistry Department MANUAL PHYSICAL CHEMISTRY III The mass of an empty weighing bottle m0: Tab. 2: The determination of the surface tension by the drop-weight method. Tab. 3: The determination of the surface tension by the drop counting method Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 7 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 2: Determination of Surface Tension Liquids by Capillary Rise Method Surface Tension Measurements In this laboratory exercise we will measure the Surface Tension of Methanol as a function of S temperature. This will allow us to determine the Surface Energy (E ) of this liquid. Also, the Surface Tension of aqueous solutions of Ethanol and n-Butanol will be measured as a function of solute concentration. Using this data, we will demonstrate that for a sufficiently dilute solution, n-Butanol, a Surface Active molecule, behaves as a Two Dimensional Ideal Gas. This data will also allow us to determine the effective cross sectional area of an n-Butanol molecule on the solution’s surface. The surface tension of a liquid is responsible for such everyday phenomena as the beading of rainwater and droplet formation and allows for the blowing of soap bubbles. It is responsible for the adhesion of liquids onto other surfaces and the contraction of surfaces to form spherical drops. The interface between a liquid and a vapor acts like an elastic balloon surrounding the liquid. In expanding the surface, molecules in the bulk must move up toward the interface. However, molecules of the liquid near the surface have a higher energy than those in the bulk because they are held in the liquid phase by fewer nearest neighbors. So, it requires work to move bulk molecules to the surface. Hence in requires work to expand the surface area (A) of the liquid. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 8 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Formally, the surface tension () is defined in terms of the Work (W) required to expand the surface area of the liquid. Consider a liquid film enclosed by a wire loop (think of a soap film in a toy bubble blower loop) where one side of the loop is allowed to slide back and forth. A force (f) is applied to counter the contractive force due to the surface tension of the liquid. Working against the surface tension an incremental increase in the force will do work Wrev in pulling the slide out a distance dx: We define the Surface Tension in terms of this force such that: Where l is the length along the slide and the factor of “2” is required to account for the film’s two sides. (note the analogy between the intensive parameter , defined as a force per unit length, and the intensive parameter pressure, defined as a force per area.) Then we relate the surface tension to the change in area (A) of the film via: Where dA is the increase in area of the surface of the liquid film. This work is included in our expression for the Gibbs free energy; since the Free Energy is a measure of a system’s “useful or available” work, beyond PV expansion work: Temperature Dependence As per Adamson (1979,) we define the Surface Gibbs Free Energy per unit area as: Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 9 Chemistry Department MANUAL PHYSICAL CHEMISTRY III This gives us a Surface Entropy of: S S Measurably, the Surface Energy (E ) and Enthalpy (H ) are usually indistinguishable, so: It is observed that for most liquids varies roughly linearly with temperature. S The means E remains fairly constant with increasing temperature. That is, until the temperature nears S the liquid’s critical temperature (Tc) where upon E drops to zero. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 10 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Concentration Dependence We define the Excess Surface Concentration of a solute, designated as component “2”, as: Where is the number of moles of solute in a binary mixture near the solution’s surface. A positive excess surface concentration suggests the solute is congregating near the surface in levels in excess of its bulk values. The reverse is true if this quantity is negative. It is found that certain simple electrolytes give aqueous solutions with 2 < 0. On the other hand, small polar, organic molecules generate aqueous systems for which 2 > 0. In fact, solutes such as n-Butanol, which possess a polar head and a non-polar tail aggregate near the surface so as to form a monolayer. In cases such as these, increases in the bulk concentration will not change the excess surface concentration of the solute. These solutes are referred to as Surface Active. It was shown by Gibbs (Adamson 1979) that 2 for dilute binary solutions can be approximated by: Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 11 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Where C is the concentration of the solute. This relation is known as the Gibb’s Isotherm For sufficiently dilute solutions of surface active molecules, it is found that the surface tension is proportional to the concentration. o Where is the surface tension of the solvent and b is a proportionality constant. Capillary Rise Method Several methods are available for measuring the surface tension of liquids. In this laboratory exercise we will use the Capillary Rise Method for determining our desired surface tension values. This methodology employs a small bore capillary which is inserted into the liquid whose surface tension is to be determined. The height to which the liquid rises in the tube is proportional to the surface tension. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 12 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 13 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimentally, the radius of the capillary’s bore is determined by calibrating the capillary using a fluid such as Water whose surface tension is known. Once calibrated, a simple height measurement will give us the surface tension. This derivation requires the meniscus be hemispherical. This can be achieved if the glass surface is thoroughly clean. Otherwise this will not be true and (Eq. 22) will not hold exactly. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 14 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Procedures Week 1 1- Prepare solutions of solutes to be measured. These will include: 0.8M aqueous n-Butanol and 7 dilutions of this solution; each a ¾-fold dilution of the previous mix. nButanol is an irritant. Work with it in the Fume Hood. Aq. Ethanol solutions at 20, 40, 60, 80, 100 wt% 2- Be sure the capillary is soaking in Chromic Acid cleaning solution. (The capillary should be stored in Distilled Water when not is use.) Pre-Lab work: Work out a scheme for preparing about 100 mL of each of the above solutions. Week 2 1. Rinse the capillary thoroughly with Distilled Water. Also, rinse with the sample to be measured. o 2. Calibrate each capillary you will be using against Distilled Water in the 25 C Water bath. The surface o o tension of Water over a range of 20 C to 40 C is given by: With an error of 0.03%. Take at least five readings. Allow the meniscus to approach its equilibrium position from above and below. Be sure to read the position of the outside Water level. Place about 100 mL of Distilled Water in the Surface Tension apparatus. Be sure the capillary, with its measuring ruler, is snuggly fit into the stopper and insert the stopper into o the apparatus. Place the entire apparatus into the 25 C water bath. Allow it to stand for at least 10 minutes before taking any measurements. Be sure to read the correct temperature of the water bath with an immersion thermometer. o 3. Measure the surface tension of Methanol over a range of temperatures from about 0 C to o about 50 C. Each measurement should be made five times. Allow the meniscus to approach its equilibrium position from above and below, alternatively. 4. Measure the surface tension of the n-Butanol solutions. Each measurement should be made five times. Allow the meniscus to approach its equilibrium position from above and below, alternatively. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 15 Chemistry Department MANUAL PHYSICAL CHEMISTRY III 5. Measure the surface tension of the Aq. Ethanol solutions. Each measurement should be made five times. Allow the meniscus to approach its equilibrium position from above and below, alternatively. Be sure to rinse the capillary thoroughly between each measurement and that the samples have come to o equilibrium in the Water Baths. Make all the solution measurements at about 25 C. The meniscus can be difficult to see. If you force the meniscus away from its equilibrium position and watch it return, you should be able to see it more clearly. Data Analysis All results should be accompanied by an appropriate error estimate. 1. Determine the radius of each capillary used. Use a precise value for the density of Water at your working temperature. Report both the average result and the std. dev. of the mean for each capillary. 2. Determine the surface tension for Methanol at each temperature for which it was measured. Plot vs. T; your plot should include appropriate error bars. Literature results should be S S Included on your graph. Determine ( / T)P and the Surface Energy E . Include an error estimate for E . 3. Determine the surface tension for each n-Butanol solution. These solutions are dilute enough that the density can be taken as that of Water at the measuring temperature. Plot vs. C; including appropriate error bars. Identify the “dilute solution” regime. Determine and for each solution in this regime. Verify the solute on the surface is behaving as a Two Dimensional Ideal Gas by plotting vs. 1/. Now, plot vs. lnC. Again, include appropriate error 2 bars. Calculate 2, along with an appropriate error estimate. Express the result in molecules per Å . 2 Obtain the effective cross sectional area of one n-Butanol molecule in Å . Include an appropriate error estimate. Compare your result with literature values. 4. Determine the surface tension for each Ethanol solution. (Accurate solution densities will be required.) Plot vs. C; including appropriate error bars. Interpret the results. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 16 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 3: To find out the partition coefficient of iodine between carbon tetrachloride and water. Experimental 4: To find out the equilibrium constant for the tri-iodide formation. I 2 I I 3 Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 17 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 18 Chemistry Department MANUAL PHYSICAL CHEMISTRY III IODINE, IODIDE, TRI-IODIDE EQUILIBRIUM INTRODUCTION Your assignment is to study the equilibrium between the iodide ion and iodine molecule to form the tri-iodide ion in aqueous solution (reaction 1), as described by equation 2: - where aI3 represents the activity of tri-iodide which is approximately equivalent to the stoichiometric concentration of the tri-iodide ion, [I3 ] at dilute concentrations. The variables for iodine and iodide are defined in an analogous manner. Equation 3 is the Beer's law relationship for absorbance of radiation by the tri-iodide ion and will be used to determine the tri-iodide molar absorptivity and equilibrium constant for the reaction. Here A is absorbance, b is the path length of the spectrometer, and ε is the molar absorptivity coefficient, a value that is dependent on many factors including both wave length and temperature. Equation 2 can be rearranged to equation 4: Here the subscript 0 denotes the initial concentrations of the iodine and iodide species after final dilutions and before equilibrium has been attained. PRE-LABORATORY EXERCISES 1. Calculate the value for the equilibrium constant for the reaction represented by equation 1 using thermodynamic data. Use the data given in Table A. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 19 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Table A: Thermodynamic Properties in Aqueous solution at Unit Activity and 25oC. [Note that ionic properties are based on the assignment of zero value for Hfo, Gfo, and Sfo for H+(aq). Values are for an effective [1M] , i.e., unit activities can be somewhat different from 1M concentration.] [1] You will use this theoretical value later to evaluate the accuracy of your experimental value using the test suggested in your error analyses section. 2. Why is it important to use a constant temperature bath in this exercise? 3. Calculate the concentration of tri-iodide that will give an absorbance of 0.5 where the path length is 1.0 cm and the molar absorptivity is 30,000M-1cm-1. 4. The following data was measured from one iodine/iodide solution. Initially, the iodine concentration -5 -3 was 4.044 x 10 M and the iodide concentration was 2.371 x 10 M. At equilibrium, the tri-iodide -5 concentration was 2.53x10 M. What is the experimental equilibrium constant for the reaction? LABORATORY EXERCISE 1. Before coming to lab, read over the “Spectrometer Operating Instructions” and prepare any questions about using the Ocean Optic Fiber Optic UV-VIS spectrometer. Since this is the first time you’ve used the UV-VIS spectrometers in P. Chem. labs, please summarize (in your own words) these instructions in your pre-laboratory report. 2. Equation (3) is closely obeyed only when the absorbance of tri-iodide is between 0.2 and ~0.8. For this reason, you will need to find appropriate initial concentrations of iodine and iodide for this exercise. To this end, you will be using two solutions: a solution of I2 and KI that will be prepared for you and a 100 mL solution of 0.1 M KI that you must prepare. If you are unsure how to prepare this solution and calculate its concentration to at least 4 significant figures, please consult your teaching assistant or the lab supervisor! 4. Since all of the iodine comes from the pre-made stock solution, a suitable baseline level of tri-iodide (with peak absorbance close to 0.2) can be found by trial and error. Using volumetric pipets, transfer 2-7 mL of the iodide/iodine stock solution to 100 mL volumetric flasks 1 and dilute to the marks . Place these solutions in a constant temperature bath until thermal equilibrium has been reached. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 20 Chemistry Department MANUAL PHYSICAL CHEMISTRY III 5. Scan these diluted solutions to determine a spectral region where the tri-iodide absorbs (turn on the light source in the absorbance mode). Three peaks should be observed, one for the iodide and two for the triiodide (near 300 and 350 nm). Find an amount of stock solution (2-7 mL) where the absorbance of the largest peak is between 0.18 and 0.25. Note these wavelengths and also this amount of iodide/iodine stock solution! 6. Place this same amount of the iodide/iodine stock solution into several 100 mL volumetric flasks. To each flask, add between 1 mL and 10 mL of the 0.1M KI solution and dilute each to the mark with water. This should increase the absorbance of the weakest peak (why?). At least 7 of these solutions should be prepared. Leave these samples in the constant temperature bath until thermal equilibrium has been reached. 7. Scan each sample and save the spectra to a disk (floppy or CD). Re-zero the spectrometer as needed (see the Spectrometer Operating Instructions). 8. Use both of the peak absorbances (occurring at ~285 and ~350nm) to evaluate your results. Set up a spread sheet using the absorbance for each sample at each peak and use a form of iteration to minimize the relative standard deviation of your calculated K eq‘s. Do this by varying the -1 -1 value of the absorptivity constant (~20, 000M cm < ε -1 -1) < ~40,000M cm for each of the peaks. Choose one absorbance spectrum to include it in your report. Also, prepare a plot of measured absorbance as a function of initial iodide concentration and speculate on your findings. TIPS ➦ Discuss assumptions and approximations made in the theory section of your preliminary notebook. ➦ Double-check units and significant figures for ALL reported quantities. ➦ Your experimental procedure section of the preliminary report should contain more than the steps outlined in this protocol. Each experimental step (numbers 2 through 7) is performed for a reason. Include these reasons in the experiment section. For instance, consider question 2 in the pre-laboratory exercises. ➦ Ask your teaching assistant or the lab supervisor if you have any questions. ______________________ 1 To protect the integrity (i.e., concentration/purity) of the already-prepared KI/I2 stock solution, do not pipet directly from the bottle containing the stock solution, do not return used solution to the stock, and seal the bottle with Parafilm when you are finished. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 21 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 5: Determination of the Adsorption Parameters of Oxalic acid on Charcoal This experiment will demonstrate the adsorption phenomena and teach us to determine to determine the adsorption parameters. Introduction: In general, colloidal dispersions have the property of adsorbing solutes at their surfaces. Thermodynamically, such adsorption process occurs to reduce the surface free energy of the dispersion and therefore increases its stability. The degree of adsorption of a solute (adsorbate) on the adsorbent, depends on 5 factors: 1. 2. 3. 4. 5. The chemical nature of the adsorbent and the adsorbate. The specific surface area of the adsorbent. The temperature of the adsorbate The concentration of the adsorbate The pressure of the adsorbate At a constant temperature, the relation between the amount adsorbed and the concentration in a limited concentration range may be represented by one of three adsorption isotherms. These 3 adsorption’s theories were found by: Freundlich: Y = X / m =K. Ce 1/n Langmuir: Y = X / m = {(Ym.b.Ce) / (1 +bCe)} Bruner, Emmett, Teller => BET: Y = {(Ym.b’.x) / [(1-x) X [1+(b’-1)x]]} Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 22 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Where: x : weight of adsorbate in grams, adsorbed by m grams of the adsorbent.. K & n : Freundlich’s Empirical constants Ce : Equilibrium Constant Ym: Weight of the adsorbate in grams, adsorbed by one gram of the adsorbent to form a mono layer. B: Equilibrium constant of the adsorption process Adsorbate + Vacant Sites K1 Occupied Sites K2 The adsorption parameters of Freundlich K & n in Freundlich equation from the linearized equation. Log Y = Log K + 1 / n X Log Ce Therefore, a plot of Log Y (on the vertical axis) vs Log Ce should give us a straight line. The slope of this line is equal to 1 / n, and the intercept is equal to Log K, so we can evaluate K & n. The adsorption parameters of Langmuir equations. Ym & b in Langmuir equation. We have seen that Langmuir equation is: Y = X / m = {(Ym.b.Ce) / (1 +bCe)} To linearize this equation; we took the reciprocal and multiply it by Ce to get: Ce / Y = Ce / Ym + 1 / (Ym.b) Therefore, a plot of Ce / Y (on the vertical axis) vs Ce should give us a straight line. The slope of this line is equal to 1 / Ym, and the intercept is equal to 1 / (Ym.b), so we can evaluate Ym & b. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 23 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Procedure: 1. In each of the 6 Erlenmeyer flasks provided, introduce 5 g of the adsorbent (Charcoal). 2. To each of them add 5o ml of a known dilution of a standard solution of Oxalic Acid provided (e.g. 1N, 0.8N, 0.4N, 0.1N) according to the following Table: Flask 1 ml of 1N Distilled Water Normality Oxalic Acid Of Oxalic Acid 1 50 0 1N 2 40 10 0.8N 3 30 20 0.6N 4 20 30 0.4N 5 10 40 0.2N 6 5 45 0.1N 3. Shake occasionally for 15 min and set aside for half an hour to achieve equilibrium 4. Filter and reject the first portion of the filtrate after washing The receiver with it. 5. Triturate 25ml of the aliquot filtrate in each case with 0.5N Sodium Hydroxide using Phenolphthalein as an indicator (2 drops). 6. Calculate the amount adsorbed in each case and list your Result in the following table. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 24 Chemistry Department Equilibrium conc. (Ce) {(E.P X 0.0225) / volume} X 50 MANUAL PHYSICAL CHEMISTRY III Oxalic Acid Conc. Ml from 1N Oxalic ml of H20 to 50ml Initial Conc. (Ci) 1N 0.8N 0.6N 0.4N 0.2N 0.1N 50 40 30 20 10 5 0 10 20 30 40 45 2.25 Amount Adsorbed X = Ci – Ce Log Ce End Point 1.8 1.35 0.9 0.45 0.225 Y=X/m Log Y Ce / Y After calculations the table will be as follows: Data Analysis: Make the following plots. Plot 1: Y vs Ce Plot 2: Ce/Y vs Ce Plot 3: Log Y vs Log Ce Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 25 Chemistry Department MANUAL PHYSICAL CHEMISTRY III The first plot (Plot 1) shows that the adsorption phenomena deals with the occupancy at the surface and as the vacancy increases, the rate of occupancy increases, and at the end, when no more vacancy is available, the rate of occupancy will be equal to 0. The second plot (Plot 2) reflects the linearized form of Langmuir equation. It will help us finding the Langmuir adsorption parameters: Ym and b. The third plot (Plot 3) in fact, reflects the linearized form of Freundlich adsorption isotherm equation. It is useful to find the Freundlich adsorption parameters: K and n. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 26 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 6: Adsorption of acetic acid on to activated charcoal STUDY OF ADSORPTION OF ACETIC ACID ON CHARCOAL – VERIFICATION OF FREUNDLICH'S ADSORPTION ISOTHERM AIM To study the adsorption of acetic acid on charcoal and to verify the application of freundlich's adsorption isotherm. THEORY Absorption is a physical or chemical phenomenon or a process in which atoms, molecules, or ions enter some bulk phase – gas, liquid, or solid material. This is a different process from adsorption, since molecules undergoing absorption are taken up by the volume, not by the surface (in case of adsorption). Adsorption is the adhesion of atoms, ions, or molecules from a gas, liquid, or dissolved solid to a surface. It is a surface phenomena occurs due to a tendency to lower free energy and entropy. The surface of any solid or liquid is in a state of strain due to unsaturated force. To lower this strain, they try to adsorb foreign particles on the surface. Extent of adsorption depends on (a) nature of adsorbent and adsorbate, (b) nature of surface, (c) temperature and (d) concentration of adsorbate. For a given pair of adsorbent and adsorbate and at a given temperature relation between extent of adsorption and concentration is called adsorption isotherm. Freundlich's isotherm is also applicable for absorption of gases on solid surface. The empirical equation for Freundlich's isotherm is: (x / m) = K P n where 'P' is the pressure of adsorbate (i.e., gas). (x/m) = K. C But, here the equation becomes: n where 'x' is the amount of adsorbate adsorbed by 'm' gm of the adsorbent; 'C' is the concentration of adsorbate and 'K' and 'n' are constants. By taking logarithm on both sides, we get log (x) - log(m) = log K + n log C log(x) = log (m) + log K + n log C Hence, a plot of log (x) against log C will be a straight line. The isotherm is empirical and found to be valid in the low pressure (concentration) range. As pressure (or concentration) is raised departure from the equation is found. At moderate to high pressure Langmuir's isotherm is valid and at still high pressure B.E.T. Equation is valid. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 27 Chemistry Department MANUAL PHYSICAL CHEMISTRY III A different equation is more likely to describe adsorption where the adsorbate exceeds a monolayer. The Brunauer-Emmett-Teller (BET) equation is: Where Cs = concentration at which all layers are filled Kb = a coefficient Its assumptions are: Adsorbed molecules stay put Enthalpy of adsorption is the same for any layer Energy of adsorption is the same for layers other than the first A new layer can start before another is finished. The function has an asymptotic maximum as pressure increases without bound. As the temperature increases, the constants 'k' and 'n' change to reflect the empirical observation that the quantity adsorbed rises more slowly and higher pressures are required to saturate the surface. MATERIALS REQUIRED Standard Oxalic acid solution (0.1 N), NaOH solution, CH3COOH solution, Activated charcoal, Phenolphthalein indicator, Reagent Bottles (5 each), Burette (50 ml), Pipette (10 ml), Conical flask (250 ml, 100 ml), filter papers. PROCEDURE PART-I: Standardization of NaOH against standard Oxalic acid (0.1N) 1. 10ml of given 0.1N standard Oxalic acid is pipetted out into a 100ml conical flask. 2. This solution is titrated against the given unknown concentration of NaOH using 1-2 drops of phenolphthalein indicator until the end point is colorless to pale pink. 3. Tabulate the values and repeat the titration for concurrent readings and determine the concentration of supplied NaOH solution. Table 1 Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 28 Chemistry Department MANUAL PHYSICAL CHEMISTRY III PART-II: Standardization of Acetic acid using standard NaOH solution. 1. 10ml of given acetic acid solution is pipetted out into a 100ml conical flask. 2. This solution is titrated against the standard NaOH using 1-2 drops of phenolphthalein indicator until the end point is colorless to pale pink. 3. Tabulate the values and repeat the titration for concurrent readings and determine the concentration of supplied NaOH solution. Table 2 PART-III: Verification of Freundlich's Adsorption Isotherm 1. The different concentrations of the solutions are prepared in the reagent bottles of various proportions are given in the table 3 below . 2. 10 ml of the solution is pipetted out from bottle no. 1 into a conical flask and is titrated against NaOH solution using phenophthalein indicator and the reading is tabulated as 'V' ml. 3. The above process is repeated for the remaining bottles also. 4. Now, in each of these bottles, 2g of activated charcoal is added. 5. The bottles are shaken by mechanical shaker or by manual shaking using hands for about 3045 minutes and then allowed to rest for 15 minutes. 6. A small filter paper is placed on a funnel and the content of the first bottle is filtered in a 250 ml conical flask. First 3-4 ml of the filtrate is rejected. This is to saturate the filter paper. 7. 10 ml of the filtrate from bottle no.1 is pipetted out into a 100 ml conical flask and is titrated against same NaOH solution using phenophthalein indicator. 8. Repeat the titrations for concurrent readings. 9. Similarly, repeat steps 5 & 6 for the remaining bottles also. 10. The readings are tabulated and the volume of NaOH consumed before and after adsorption are to be noted for each solution and concentration of solution in moles are to be determined. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 29 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Table 3 OBSERVATIONS AND CALCULATIONS o Room Temperature = __________________ C. Amount of Charcoal added, m = _________gm. Hence, a plot of log (x) vs log C1 gives a straight line, where 'x' is the extent of adsorption in terms of difference in concentration of solutions and 'C1' is the concentration of each solution before adsorption. The slope (n) and intercept (log K) are to be determined from the graph. COMMENTS AND DISCUSSIONS The success of the above experiment requires patience on the part of the student, because attainment of adsorption equilibrium and also subsequent filtration is a very slow process as impatience may bring error in the experiment. Care should be taken while preparing the solutions and shaking the bottles also. Each and every calculation of the tables should be shown clearly with formulas, units, graph etc. RESULT Strength(Concentration) 1. of NaOH = __________________ Strength 2. (Concentration) of AcOH = __________________ The 3. value of the constant, n = __________________ The 4. value of the constant, K = __________________ Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 30 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 7: Catalytic Decomposition of Hydrogen Peroxide on Metal Oxide Catalysts Catalytic Decomposition of Hydrogen peroxide Theory: Hydrogen peroxide solution decompose spontaneously liberating Oxygen in accordance with, H2O2 → H2O + ½ O2 The decomposition rate is markedly accelerated by solid such as Manganese dioxide, potassium dichromate, or colloidal platinum, which act as a catalyst. The course of reaction may be followed either by titrating the peroxide with potassium permanganate in acid medium or by collecting the oxygen gas evolved. There are two types of catalysis 1-Homogeneous catalysis 2-Heterogeneous Catalysis Object: Determination of the reaction rate of catalytic decomposition of hydrogen peroxide. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 31 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Materials and Equipments:hydrogen peroxide ( H2O2), H2SO4 , KMnO4 , manganese dioxide ( MnO2, potassium dichromate , beaker , 2 conical flasks , burette, pipette , Stopwatch. Part 1:Homogeneous Catalytic decomposition of H2O2 by using K2Cr2O7 solution Procedure 1- Prepare 250 ml 0.1N KMnO4 . 2- Prepare 250 ml 1.2 % H2O2 solution (10 volumes H2O2 is nearly equal3%). 3- Thermostat the solution of H2O2 at 30ºC for 20 min. 4- Add 3 ml of K2Cr2O7 catalyst and record the time. 5- Pipette out 10 ml of the decomposed mixture into a flask containing ( 10 ml of 2N H2SO4) and titrate rapidly with 0.1 N KMnO4. 6- Repeat step (5) at increasing time intervals extending for about 90 min. 7- Repeat the experiment from the beginning using 5 ml K2Cr2O7, 8- Tabulate your results as follows: (t) : Calculated from start adding manganese dioxide, and in addition to the last minutes. (a-x) : is the concentration of H2O2 that not decomposed, expressed in ml of the permanganate size that consumed in each titration . Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 32 Chemistry Department Time Volume KMnO4 used Vt = ( a – x) 3 ml catalyst 5 ml catalyst MANUAL PHYSICAL CHEMISTRY III Log(Vt) = log (a-x) 3 ml catalyst 5 ml catalyst 3 7 10 20 30 45 60 75 90 Calculate k and t½, where .k = -slope x 2.303 t½ = 0.963 /k Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 33 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Part 2 :Heterogeneous Catalytic decomposition of H2O2 by using MnO2: Procedure 1- Prepare 250 ml from solution KMnO4 (0.1N). 2- Prepare 250 ml from H2O2 solution. 3- Thermostat the solution of H2O2 at 30ºC for 20 min 4- Mix 100 ml of (1.2%) H2O2 solution and 0.05 gm. from MnO2. 5- Pipette out 10 ml of the decomposed mixture into a flask containing (10 ml of 2N H2SO4) and titrate rapidly with 0.1 N KMnO4. 6- Repeat step (5) at increasing time intervals extending for about 90 min. 7- Tabulate your results as follows : Data Time Volume KMnO4 used log(Vt) = log (a-x) Vt = ( a – x) 3 7 10 20 30 45 60 75 90 Calculate k and t½ where k = -slope x 2.303 t½ = 0.963 /k Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 34 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Catalysts for the decomposition of Hydrogen peroxide Topic Reaction rates, catalysis, enzymes. Timing About 5 min. Level Pre-16. Description Several measuring cylinders are set up each containing a little washing up liquid and a small amount of a catalyst for the decomposition of hydrogen peroxide. Hydrogen peroxide is poured into the cylinders and a foam rises up the cylinders at a rate that depends on the effectiveness of the catalyst. Apparatus _ Several 250 cm3 measuring cylinders – one for each catalyst to be used. _ A large tray to catch any foam that spills over the top of the cylinders. _ Stopwatch or clock with second hand. Chemicals The quantities given are for one demonstration. _ 75 cm3 of 100 volume hydrogen peroxide solution. _ About 0.5 g of powdered manganese(IV) oxide (manganese dioxide, MnO2). _ About 0.5 g of lead(IV) oxide (lead dioxide, PbO2). _ About 0.5 g of iron(III) oxide (red iron oxide, Fe2O3). _ A small piece (about 1 cm3) of potato. _ A small piece (about 1 cm3) of liver. Method Before the demonstration Line up five 250 cm 3 measuring cylinders in a tray. Add 75 cm 3 of water to the 75 cm3 of 100 volume hydrogen peroxide solution to make 150 cm 3 of 50 volume solution. The demonstration Place about 1 cm 3 of washing up liquid into each of the measuring cylinders. To each one add the amount of catalyst specified above. Then add 25 cm 3 of 50 volume hydrogen peroxide solution to each cylinder. The addition of the catalyst to each cylinder should be done as nearly simultaneously as possible – using two assistants will help. Start timing. Foam will rise up the cylinders. The lead dioxide will probably be fastest, followed by manganese dioxide and liver. Potato will be much slower and the iron oxide will barely produce any foam. This order could be affected by the Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 35 Chemistry Department MANUAL PHYSICAL CHEMISTRY III surface areas of the powders. Time how long each foam takes to rise to the top (or other marked point) of the cylinder. The foam from the first three cylinders will probably overflow considerably. Place a glowing spill in the foam; it will re-light confirming that the gas produced is oxygen. Teaching tips Some students may believe that the catalysts – especially the oxides – are reactants because hydrogen peroxide is not noticeably decomposing at room temperature. The teacher could point out the venting cap on the peroxide bottle as an indication of continuous slow decomposition. Alternatively s/he could heat a little hydrogen peroxide in a conical flask with a bung and delivery tube, collect the gas over water in a test-tube and test it with a glowing spill to confirm that it is oxygen. This shows that no other reactant is needed to decompose hydrogen peroxide. NB: Simply heating 50 volume hydrogen peroxide in a test-tube will not suceed in demonstrating that oxygen is produced. The steam produced will tend to put out a glowing spill. Collecting the gas over water has the effect of condensing the steam. It is also possible to ‘cheat’ by dusting a beaker with a tiny, almost imperceptible, amount of manganese dioxide prior to the demonstration and pouring hydrogen peroxide into it. Bubbles of oxygen will be formed in the beaker. Theory The reaction is : 2H2O2(aq) 2H2O(l) + O2(g) This is catalysed by a variety of transition metal compounds and also by peroxidase enzymes found in many living things. Extensions Repeat the experiment but heat the liver and the potato pieces for about five minutes in boiling water before use. There will be almost no catalytic effect, confirming that the catalyst in these cases is an enzyme that is denatured by heat. Investigate the effect of using lumpy or powdered manganese dioxide. The powdered oxide will be more effective because of its greater surface area. Try using other metal oxides or iron filings as catalysts. Animal blood may be used instead of liver if local regulations allow this. One teacher suggested measuring the height of the foam over suitable time intervals and plotting a graph. Further details The experiment can be done with 20 volume hydrogen peroxide, but is less spectacular. It is, however, easier to time. It has been suggested that manganese dioxide is not in fact the catalyst for this reaction, but that the catalysts are traces of other oxides found on the surface of manganese dioxide. Safety Wear eye protection. Used liver should be wrapped up in paper and placed in the dustbin. It is the responsibility of teachers doing this demonstration to carry out an appropriate risk assessment. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 36 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 8: Catalytic Decomposition of Hydrogen Peroxide on MnO2 Decomposition of Hydrogen Peroxide by Various Catalysts Equipment: 3 goblets measuring cylinders spatula (food grater 200-mL Erlenmeyer flask cheese cloth or cotton tea filter beaker) Chemicals: Hydrogen peroxide solution (6%) iron(III) chloride solution (0.1 M) manganese dioxide powder catalase solution (1%) or crude potato extract (Peeled raw potato deionised water crushed ice) Safety: Hydrogen peroxide solution (H2O2): Xn R22-41 S26-39 manganese dioxide (MnO2): Xn R20/22 S25 iron(III) chloride (FeCl3): Xn R22-38-41 S26-39 Xn It is necessary to wear safety glasses and protective gloves, because every contact with eyes or skin should be avoided. Procedure: Preparation of crude potato extract: Approx. 20 g of peeled raw potato are finely grated by means of a food grater. The paste is scraped into a 200-mL Erlenmeyer flask and 25 mL icecooled deionized water are added. The flask is swirled in intervals for about 15 min. Subsequently, the suspension is filtered through a sheet of cheese cloth or a cotton tea filter into a chilled beaker. Procedure: 20 mL hydrogen peroxide solutions are filled into each of the three goblets. Homogeneous catalysis: 2 mL iron(III) chloride solution are added to the first goblet. Heterogeneous catalysis: A spatula-tip full of powdered manganese dioxide is added to the second goblet. Enzymatic catalysis: 1 mL catalase solution or alternatively 2 mL of the filtered clear potato extract are added to the third goblet. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 37 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Observation: Homogeneous catalysis: The color of the solution changes from pale yellow to brownish orange. Additionally, a noticeable formation of gas can be observed after a while. The pale yellow color returns together with the end of bubbling. Heterogeneous catalysis: A strong effervescence combined with the formation of fog can be observed (therefore, the experiment is also known as “genie in a bottle”). The liquid gets dark because of the finely dispersed black manganese dioxide and the goblet warms up considerably. Enzymatic catalysis: In the case of the catalase solution a strong evolution of gas takes places and the goblet gets warm. The reaction catalyzed by the catalase from potato extract is weaker and a distinct foam layer is formed. Explication: Hydrogen peroxide in aqueous solution exhibits a strong tendency to decompose into water and oxygen (disproportionation): The decomposition rate at room temperature is, however, immeasurably small. But the rate can be appreciably increased by the addition of a catalyst. 3+ Fe ions are an example for a homogeneous catalyst, i.e. the catalyst is in the same phase as the reaction mixture. The catalytic decomposition of hydrogen peroxide can be essentially explained by two different mechanisms based on the mutual redox transition Fe(III)/Fe(V) (KREMER-STEIN mechanism) and Fe(III)/Fe(II) (HABER-WEISS mechanism), respectively. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 38 Chemistry Department MANUAL PHYSICAL CHEMISTRY III According to the mechanism proposed by KREMER and STEIN intermediate oxygen complex of 3+ iron with oxidation number +V is primarily formed by the reaction of Fe with H2O2. This complex reacts with another H2O2 molecule to water and oxygen thereby re-forming 3+ Fe . 3+ According to the mechanism proposed by HABER and W EISS the Fe ions initiate a radical reaction, after which the chain reactions consume the hydrogen peroxide. This mechanism can explain the high reaction rates very well. Chain initiation:Fe 3 Chain propagation: Fe Fe 3 III 2 H2 O2 R [Fe OOH] 2 H2 O2 → Fe 3 H2 O2 OH· → Fe H R Fe 2 HOO· H 2 OH 3 HOO· H2 O → Fe 2 H O 2 H2O Mangan dioxide is an example for a heterogeneous catalyst, i.e. the phase of the catalyst is different from that of the reaction mixture. The surface of solid manganese dioxide provides a particulary favourable environment to catalyze the decomposition, though the mechanism is not understood very well. For increasing the surface area available for contact with the hydrogen peroxide solution a finely graded powder is used. The observed fog (the “genie”) is caused by condensing water vapour mixed with oxygen gas. Enzymatic catalysis takes an intermediate position, because enzymes are proteins, i.e. macromolecules with diameters between 10 and 100 nm, that are colloidally dispersed in solution and mostly much bigger than the substrate molecules. The cytoxin hydrogen peroxide is one of the by-products of many cellular reactions. Aerobic cells protect themselves against peroxide by the action of the enzyme catalase. Therefore, catalase is nearly ubiquitous among animal organisms, especially it is found in liver and red blood cells. But catalase also occurs in plant tissues, and is especially abundant in plant storage organs such as potato tubers, corms, and in the fleshy parts of fruits. The detailed structure of catalase differs from one organism to another, but the general quaternary structure is analogous to hemoglobin in that catalase is tetrameric and each polypeptide chain, composed of more than 500 amino acids, contains an iron-centered porphyrin ring. However, in contrast to hemoglobin, catalase utilizes Fe(III). This iron can formally be oxidized to Fe(V) in the oxidation-reduction cycle, but the processes at the active site of the enzyme are not understood very well. But the incorporation of the iron ions in the porphyrin and in the enzyme protein improves apparently their catalytic activity because the effect of catalase is much stronger than that of the iron ions in solution. Disposal: Hydrogen peroxide solutions can be disposed of down the drain with running water. Manganese dioxide can be reused after drying. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 39 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 9: Traffic lights Traffic lights A catalyst increases the rate of a chemical reaction without itself being permanently changed by the reaction. The emphasis on permanently changed is important when discussing homogeneous catalysis because the catalyst does undergo chemical change in providing an alternative reaction pathway of lower energy. The ability to change oxidation state for transition metals makes them suitable as homogenous catalysts. A new activated complex is formed with the catalyst because transition metals can form stable compounds in more than one oxidation state and the transition metal ions can therefore readily move between oxidation states. During the catalysed reaction the transition metal (TM) ion is oxidised by one reactant to a higher oxidation state. This is then reduced back to the original form by reaction with the other reactant. The reactants are therefore converted to the same products as are formed without the catalyst. The only difference is that the reactants are converted into products more quickly. Reactant 1 + TM ion in low oxidation state Reactant 2 + TM ion in high oxidation state Product + TM ion in high oxidation state Product + TM ion in low oxidation state In this simple demonstration, potassium sodium 2,3-dihydroxybutanedioate or potassium sodium tartrate (Rochelle salt) is oxidised by hydrogen peroxide in the presence of cobalt(II) ions. You simply mix the hot reactants and add the catalyst. C4H4O62- (aq) + 3H2O2(aq) 2CO2(g) + 2HCO2-(aq)+ 4H2O(l) The interesting feature of this reaction is the colour change which occurs as the reaction proceeds. The initial colour is pink which changes to dark green and then back to pink again - hence the traffic light reaction. When you see the coloured intermediate, you can try to stabilise it by cooling the mixture rapidly. The nature of this intermediate can lead to some stimulating discussion about colour, thermodynamic and kinetic stability. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 40 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Kit Gloves; spatula; Beaker, 250cm3; measuring cylinder, 25cm3; Distilled water; thermometer (0-100°C); Bunsen burner and mat; tripod and gauze; Stirring rod; teat pipette; two test tubes and rack; Potassium sodium 2,3-dihydroxybutanedioate, CO2K(CHOH)2CO2Na.4H2O (also known as potassium sodium tartrate (Rochelle salt), 1g; Hydrogen peroxide (20 vol), 20cm3; Cobalt(II) chloride, CoCl2.6H2O , 0.25g. Procedure Dissolve ca 1g of potassium sodium 2,3-dihydroxybutanedioate in ca 50cm3 of water in a beaker. Heat the solution to about 70°C. Add ca 20cm3 hydrogen peroxide solution and reheat to 70°C. Note any sign of a reaction. Dissolve ca 0.25g of cobalt(II) chloride in 5cm3 distilled water in a test tube and add to the hot reaction mixture. There will be an induction period before the reaction proceeds. As soon as the solution appears dark green, quickly transfer a small portion, using a teat pipette, into a test tube which is placed in a salted ice-bath. Safety Potassium sodium 2,3-dihydroxybutanedioate is an irritant. Hydrogen peroxide is corrosive. Hydrated cobalt(II) chloride is toxic. The dust may be irritating and, in larger doses, severely damaging to the respiratory tract. Skin contact, inhalation or ingestion should be avoided. Special tips If the reaction gets too hot or the reactants are too concentrated, effervescence from the reaction could cause the mixture to spill out of the beaker. Teaching goals This experiment can lead to a full-scale kinetic investigation by changing the concentration of the reactants and the catalyst. It can be used to develop a deeper understanding of non-standard electrode potentials and their use in predicting the feasibility of a reaction: 2HCO2-(aq) + 2CO2(g) + 6H+(aq) + 6eC4H4O62- (aq) + 2H2O(l) E = +0.20V H2O2(aq) + 2H+(aq) + 2e2H2O(l) E = +1.77V The reaction is energetically favourable because E is +1.57V, which is large enough for the reaction to go to completion. However, being thermodynamically feasible does not mean the reaction is kinetically favourable and the reaction is very slow even when heated because of a high kinetic barrier. The catalyst will provide an alternative reaction pathway with a lower activation energy. H2O2(aq) + 2H+(aq) + 2Co2+(aq) 2H2O(l) + 2Co3+(aq) C4H4O62-(aq) + 2H2O(l) + 6Co3+(aq) 2HCO2-(aq) + 2CO2(g) + 6H+(aq)+ 6Co2+(aq) For this mechanism to work, the standard electrode potential (SEP) for the Co3+/Co2+ half-cell must lie within a certain range of values as indicated above (+0.20 V to +1.77V). However, the SEP for the halfcell Co3+ (aq), Co2+ ( aq) | Pt is +1.84V. At first glance, you might think that in non-standard conditions this value is not that far out of the range required, but concentration or temperature changes Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 41 Chemistry Department MANUAL PHYSICAL CHEMISTRY III do not alter E values very much. The main reason is cobalt ions can form complexes with the 2,3dihydroxybutanedioate ions - a bidentate ligand. Electrode potentials for half-cells involving complexes are often substantially different from those involving simple ions. This is another fruitful area for discussion (crystal and molecular orbital theory). Unfortunately the value for this half-cell is not quoted in the literature but even if it were shown to be energetically favourable, there would still be no way of knowing whether the reaction was kinetically favorable. You would have to do this experiment to find out. Finally, you should note that cobalt(II) catalysis the decomposition of hydrogen peroxide into water and oxygen and the equations written here do not take that into account. Clearly, this side reaction will influence any thermodynamic or kinetic discussion with this reaction. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 42 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 10: To make a colloid and demonstrate its properties SOLUTIONS AND COLLOIDS OBJECTIVES 1. To examine the influence of solvent and solute on solution formation 2. To prepare a solution for use in a later experiment 3. To make a colloid and demonstrate its properties INTRODUCTION Part I. Influence of solute and solvent on solubility Solutions are homogeneous mixtures of two or more chemical substances. The components can be gases, liquids, or solids, and they are uniformly distributed. As a result, the properties of a true solution are the same throughout the solution. The component of a solution that produces dissolution is called the solvent and is often present in greater proportion. The component that is dissolved is called the solute. The components of the solution are of atomic or molecular size. Thus they are too small to reflect light and solutions will be transparent, though they may be colored or colorless. Often, then, it becomes necessary to use chemical and physical tests to identify a substance as a solution rather than as pure solvent. Chemical tests, such as the formation of a precipitate (studied in the experiment on chemical reactions), are frequently used to identify ions or molecules in a solution. The solubility of a solute in a particular solvent is a property of that solute. Commonly, the solubility of a solute in a liquid is reported in grams of solute per 100 mL of solvent. Several factors may influence the solubility of a solute, including temperature, the nature of the solute, and the nature of the solvent. To understand how the nature of the solute and solvent affect solubility, the concept of intermolecular forces must be examined. These are the forces of attraction among particles, and they exist among solute particles and among solvent particles. In order for a solute particle to dissolve, its interactions with other solute particles must be overcome and new interactions with the solvent must form. This happens most readily when intermolecular forces between solute and solvent are similar. If the interactions between solute particles are stronger than those between solute and solvent, the solute will not dissolve. Thus polar covalent and soluble ionic compounds are soluble in polar solvents such as water, and insoluble in nonpolar solvents such as benzene and carbon tetrachloride. Nonpolar covalent compounds, on the other hand, are much more soluble in nonpolar solvents than in polar solvents. Thus the general rule-of-thumb is "like dissolves like". Soluble substances dissolve completely in the solvent and form solutions. Insoluble substances do not dissolve in the solvent. Two liquids that are completely soluble in each other are called miscible. When a liquid solute doesn't dissolve in a liquid solvent, but instead forms a separate layer, the liquids are said to be immiscible. In Part I of this experiment, you will test the solubility of a series of compounds in two solvents, one polar and one nonpolar. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 43 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Part II. Preparation of a solution Since many of the reactions carried out in laboratories and all of those in our bodies take place in solution, it is necessary to be able to determine the concentration of the solute, or the relationship between the quantities of solute and solvent found in solutions. Concentrations can be given in many units, but one of the most commonly used in chemistry is molarity. Concentration expressed as molarity gives the relationship between the number of moles of solute and the volume of solution. It is defined as: In order to make a solution of a given molarity, you can weigh out a calculated amount of solute and dissolve it in enough solvent to make the desired volume of solution. For example, to make 100.0 mL of a 0.100 M NaCl solution, you need: This requires you to weigh out: To prepare the solution, you would weigh out 0.585 g of NaCl, add enough water to dissolve, then dilute to a total volume of 100.0 mL using a 100 mL volumetric flask. To calculate the concentration of a solution prepared from a known mass of solute, you must find the number of moles of that solute, then divide by the total volume of solution. For example, if you weigh out 0.784 g of NaCl and dissolve it in a total volume of 150.0 mL: In Part II, you will prepare a solution and determine its concentration for use in a subsequent experiment. Part III. Colloids Part III of this experiment examines colloids. Colloidal suspensions consist of a dispersing medium and a dispersed material. These can be solids, liquids, or gases. The dispersed material exists as particles that are much larger than those in a true solution. Though they are small enough to remain suspended in the dispersing medium, they are large enough to scatter light when an intense beam of light passes through the suspension. This property of colloids is called the Tyndall effect. Some examples of colloids include milk (a liquid dispersed in a liquid), smoke (solids in a gas), whipped cream (a gas in a liquid), and fog (a liquid in air). In Part III, you will compare a solution and a colloid, using the Tyndall effect to test for the presence of the colloid. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 44 Chemistry Department MANUAL PHYSICAL CHEMISTRY III PROCEDURE Part I. Influence of solute and solvent on solubility A. Place 8-10 drops of water in each of 9 test tubes. Then add the following solutes and test for solubility. For solids, add a few crystals. For liquids, add 8-10 drops. Shake to mix and record your observations. a. methanol (CH3OH) b. ethanol (CH3CH2OH) c. n-propanol (CH3CH2CH2OH) d. n-butanol (CH3CH2CH2CH2OH) e. NaCl f. table sugar (C12H22O11) g. oil (mixture of compounds containing mostly carbons and hydrogens) h. MgSO4 i. n-octanol (CH3CH2CH2CH2CH2CH2CH2CH2OH) B. Repeat the experiment, using 8-10 drops of oil in each test tube instead of water. Part II. Preparation of a solution CAUTION: SODIUM HYDROXIDE IS A STRONG BASE. IF IT COMES INTO CONTACT WITH SKIN, FLUSH IMMEDIATELY WITH LARGE VOLUMES OF WATER. 200 mL of an approximately 0.1 M NaOH solution will be prepared. Weigh out between 0.7 and 1.0 g of NaOH on the laboratory balance, recording the exact weight. Add to a 200 mL volumetric flask along with enough water to dissolve. Then fill the flask to the mark with water. Mix thoroughly. Part III. Preparation and testing of a colloid Dissolve two small crystals of sodium thiosulfate in 5 mL of deionized water in a large clean test tube. Check the solution for the Tyndall effect by holding the test tube in the path of the light from one of the lamps located in the lab. Remember, if you have a true solution it should not exhibit the Tyndall effect. If you notice the scattering of light, it is probably dust particles and your test tube needs to be recleaned. Next, add 10 drops of 6 M HCl to the solution of sodium thiosulfate. The reaction which occurs should generate a colloidal suspension of sulfur in water. The reaction equation is Now, check the mixture for the Tyndall effect again. Note: sometimes it requires a few minutes for the Reaction to begin. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 45 Chemistry Department SOLUTIONS AND COLLOIDS LABORATORY REPORT MANUAL PHYSICAL CHEMISTRY III NAME __________________________ DATE __________________________ Part I. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 46 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 47 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Part II. Mass of NaOH + paper: ________ Mass of paper ________ Mass of NaOH ______ Part III. Observations Thiosulfate solution: Thiosulfate + HCl: Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 48 Chemistry Department MANUAL PHYSICAL CHEMISTRY III QUESTIONS Part I. 1. Methanol, ethanol, propanol, butanol, and octanol are in a class of compounds called alcohols. Given the following information, prepare a graph of the number of carbon atoms in the compound vs. the boiling point of the compound. Be sure to use the rules for graphs given in Lab 7. Do you see a relationship? What is it? 2. Which compounds are soluble in water? In oil? 3. What is the relationship between the number of carbon atoms in an alcohol and its solubility? 4. Predict whether ethanol will be soluble in propanol and justify your prediction. Part II. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 49 Chemistry Department MANUAL PHYSICAL CHEMISTRY III 5. Calculate the molarity of your solution of NaOH, using the weight obtained in Part II. Show all your work and be sure to give your answer with the appropriate number of significant figures. (Volumetric glassware measures volume to 4 significant figures.) Part III. 6. Was the thiosulfate before addition of HCl colloidal or a true solution? How do you know? What about after addition of HCl? 7. Explain why you should use your low beam headlights in foggy weather. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 50 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 11: Stability of the emulsions Stability of Emulsions Introduction In this activity we will compare the stability of oil and vinegar emulsions with various Additives. Material 6 Test tubes Test tube rack Oil Vinegar Egg yoke Milk Cayenne pepper Mustard (ground) Glyceryl Monstearate (GMS) To Do and Notice Place 6 test tubes in a test tube rack. Measure out equal volumes of oil and vinegar into each tube. Label the test tubes 1 through 6 and add the following ingredients: 1. No additions 2. ¼ teaspoon egg yoke 3. ¼ teaspoon milk 4. ¼ teaspoon cayenne pepper 5. ¼ teaspoon ground mustard 6. ¼ teaspoon GMS Cover and shake each test tube approximately 100 times and place in the test tube rack. Compare the stability and thickness of each emulsion immediately after shaking and After letting the solution sit for 10 minutes. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 51 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Which additives formed stable emulsions? Which additives formed temporary emulsions? Which additive formed the thickest emulsion? What’s going on? Oil and water do not mix. An emulsion is a stable mixture of to liquids that do not normally mix such as oil and water, or oil and vinegar. Mayonnaise and Hollandaise sauce are common emulsions, as well as homogenized whole milk (a mixture of butter fat or cream and milk). In order to form a stable mixture of two repelling liquids, you need an emulsifying agent, which will prevent the oil droplets or fat from coalescing and separating from the opposing liquid. Emulsifying agents perform two duties. They coat the oil droplets with like charges and reduce the surface tension of the water or vinegar. This reduces the waters ability to repel oil, and reduces the oils ability to recombine to form larger oil droplets. Egg yokes contain Lecithin, an emulsifying agent as used in Mayonnaise and Hollandaise Sauce. Milk contains the protein casein which acts as a natural emulsifier. Other natural emulsifiers are mustard and cayenne pepper. Commercial sauce manufacturers use industrial emulsifiers such as monoglycerides and diglycerides that don’t add flavor, but chemically emulsify the solution. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 52 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 12: To find the critical point for colloidal mixtures composed of different types of starches. Abstract What is a colloid? If you have made Oobleck out of corn starch and water, then you know that a colloid is a mixture that acts like a solid and a liquid at the same time! What is the critical factor to making a colloidal material? Will different sources of starch change the recipe? Objective The purpose of this project is to find the critical point for colloidal mixtures composed of different types of starches. Introduction What do ketchup, Oobleck, and quicksand have in common? They are all made up of tiny, solid particles suspended in water. Chemists call this type of mixture a colloidal suspension, and the amount of solid and water to use is called the critical concentration. The critical concentration for each colloidal material is unique and depends on many different factors. Colloids have very interesting physical properties. One of the more interesting physical properties of colloidal materials is that sometimes they seem to be solid and other times they seem to be a liquid. Because of this odd behavior, colloids are called non-Newtonian fluids, because they break the rules of ideal fluids described by Isaac Newton in the 1700's. Colloidal suspensions respond differently to different forces, as seen in this cool Oobleck video by Blake (Kids Science, 2006). A fast, hard force will cause the colloid to appear solid, but a slow, even force will cause the colloidal material to flow like a liquid. This can be dangerous if you live in an area with clay soil, because sideways forces during a flood or earthquake can cause the earth to suddenly become very unstable! As it turns out, colloidal materials are very common. Even though they have such strange physical properties, those same properties make them very useful products and materials. Foam, gel, glue, and clay are all examples of colloidal materials. There are many colloidal materials found in food products, like: marshmallows, mayonnaise, pudding, milk, butter, and jelly. Building materials like cement, stucco, plaster, and paint are colloidal materials. Even our bodies and other living organisms are made of colloidal materials! They are everywhere! In this experiment, you will learn about a very simple colloidal material, starch suspended in water. You will test starch from different plant sources (corn, potato, rice, tapioca) to see if the colloids share similar physical properties. You will measure the amount of water needed to make a colloid out of each type of starch. Will these colloidal suspensions be the same or different? Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 53 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Terms and Concepts To do this type of experiment you should know what the following terms mean. Have an adult help you search the internet, or take you to your local library to find out more! starch colloid physical properties solid liquid Questions How does starch behave as a colloidal material? What are the physical properties of colloidal materials? Do different sources of starch change the properties of the colloid? Bibliography Exploratorium, 1998. "Science Explorer: Outrageous Ooze — Is This Stuff a Liquid or a Solid?," San Francisco: Exploratorium. [accessed July 3, 2006] http://www.exploratorium.edu/science_explorer/ooze.html Watch this video to see Blake explain how to make Oobleck, show you its physical properties, and talk about matter: Kids Science, 2006. "Kids Science Episode 1: Cornstarch Suspension," YouTube.com [accessed July 18, 2006] http://www.youtube.com/watch?v=fazPiaHvFcg Watch this video to see how high frequency waves cause very odd behavior in Oobleck, from this paper by researchers at the Center for Nonlinear Dynamics, University of Texas at Austin: Merkt, F.; Deegan, R.D.; Goldman, D.; Rericha, E., and Swinney, H.L., 2004. "Persistent holes in a fluid," Phys. Rev. Letters. 92 184501 [accessed July 3, 2006] http://chaos.ph.utexas.edu/research/vibrated_cornstarch.htm Seuss, 1949. Bartholomew and the Oobleck, New York: Random House. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 54 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Materials and Equipment water cups measuring spoons medicine dropper or small syringe stir stick different types of starches: o corn starch o potato starch o tapioca starch o rice starch Experimental Procedure 1. You will need to determine the amount of water required to form a colloid from each type of starch, one at a time. 2. Starting with the corn starch, add 1 tbsp of the starch to a small cup or bowl. 3. Add water one drop at a time, stirring frequently and counting the number of drops until the mixture forms a colloid. You will recognize the colloid when you stir with your stir stick. At first, the mixture will look solid and separate into clumps, but then the clumps will start to flow together again like a liquid. 4. When you reach the proper consistency for a colloid, stop adding water and record the number of drops in a data table: 5. Play around with the colloidal material. Poke it with your finger and put some in your hand. What does it look like? How does it move? What does it feel like? Write down some of the physical properties in your data table. 6. Repeat steps 2–5 with each of the other starches and record your data in the data table. 7. Make a bar graph of your data to compare the different starches. Place the number of drops of water on the left side (Y-axis) of the graph. Draw a bar for each type of starch up to the matching number of drops. Compare the bars on the graph representing the different starches. Are they the same or different? Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 55 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Variations Experiment with the different properties of the colloids. Are they solid or liquid? Do they respond differently to different kinds of pressure? Push slowly into the colloid with your finger. How does the colloid respond? Poke the colloid hard with your finger. Does it respond differently? Do all of the colloids respond similarly and have similar properties? Can you find other ways of testing the physical properties of colloidal materials? Starches are often used to make gels. What happens if you increase the temperature of your colloidal material? Try heating up the colloidal starch mixtures. How do they change? Are there new physical properties that you can observe? Do starches from different plant sources gel at the same temperature and have the same consistency? For more on gels, try the Science Buddies project Are You Gellin'? Clay earth behaves like a colloidal material when it has just the right amount of water in it. Can you find the critical amount of water needed to made a colloidal clay soil? Colloids can appear solid against strong downward forces, but are very weak against lateral forces that push sideways. Try testing your colloid against these two different directional forces. Which direction is your colloid the weakest? If your colloid were a clay soil, how would this contribute to landslides or earthquakes? Can you engineer a way to make colloidal soils resistant to lateral forces during earthquakes and landslides? Tell Us About Your Experience If you completed this project, please help Science Buddies by letting us know how things went! Fill out our I Did This Project form to submit your comments. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 56 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 13: Find out the formula of cupper ammonia complex Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 57 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 58 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 59 Chemistry Department MANUAL PHYSICAL CHEMISTRY III Experimental 14: Surface tension of n-butanil solution Introduction After being amazed by the apparent “magic” of water’s high surface tension as children, most of us think little of the consequences of this interesting property of liquids. Surface tension plays a part in many common effects seen every day: a water stream breaking into droplets and the beading of water on a smooth, non-polar surface are just two examples. In this lab, we became closely acquainted with the surface tension of an aqueous solution and what effects it had on surface concentration. We combined pure n-butanol with water in various concentrations to see how much effect it would have on the surface tension. Plotting the value of gamma (surface tension) in units of g/s2 for each of the concentrations presented a linear relationship. The slop of the line gave us what we needed to find the surface concentration using the Gibbs isotherm equation. Finally, we used this value to find an experimental molecular crosssectional area which we compared to a theoretical one using computer-built molecular models. Real-world applications of surface concentration and surface tension might be found in industries requiring precise control on fluid dynamics or homogenous distribution of solutes in solution. Molecular cross-sectional area has implications in molecular collisions and the energy found therein. Experiment and Data For this experiment, we were charged with measuring the surface tension of aqueous solutions of n-butanol. This Experiment spanned over the space of two lab periods; during the first period we became acquainted with the Instrument and made the solutions and during the second we took measurements. On the first day, we started by cleaning the sensor wire. We carefully removed the wire from its hanger and used a kim wipe soaked in methanol. After this, we wiped the glass surface tension tray with methanol and let it air dry. The instrument used was a DeltaPi Single-Channel Microtensioner made by Kibron Inc. In order to calibrate the sensor,we filled one of the compartments with deionized water and submerged the sensor wire by turning the knob to lower the sensor arm. Once the tip was submerged, we slowly raised the wire out until it was visibly pulling the surface of the water up. We opened the Delta Graph program and clicked on the "Measure" button. We were calibrating with water so the Tension difference was set at 72.8 mN/m. Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 60 Chemistry Department MANUAL PHYSICAL CHEMISTRY III We clicked on "Calibrate" and the software guided us through the process (sensor in air, take reading, sensor in water, take reading). The readings were as follows: Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed Page 61 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 62 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 63 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 64 Chemistry Department Prepared by Lecturer Sahar Mahmoud Supervisor Dr. Samah A. Ahmed MANUAL PHYSICAL CHEMISTRY III Page 65