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Ch.11 notes – P.1 Ch.11 – Intermolecular Forces A. Introduction For molecular substances, the ___________________________ (covalent bonding) between atoms are strong, but the ______________________________ between molecules are weak. There are two types of intermolecular forces: 1. _________________________________________ 2. _________________________________________ B. Van der Waals’ forces It consists of three types of intermolecular attractions: 1. Dipole-dipole interactions Polar molecules have _______________________________________. They tend to orientate themselves in such a way the attractive forces are maximized. Fig. 11-4 2. Dipole-induced dipole interactions When a non-polar molecule approaches a polar molecule, a dipole will be ___________ in the non-polar molecule. Fig. 11-5 3. Instantaneous dipole-induced dipole interactions It seems that there do not exist any forces between non-polar molecules. However, non-polar molecules, even noble gases can be solidified at low temperature and under high pressure. For non-polar molecules / atoms, the electron cloud distribution is generally ____________________. At any particular moment, it is likely to be ______________________________ ___________. Thus, it possesses an _____________________________________. The instantaneous dipole moment will ____________________________ in the neighbouring atom, hence an attractive force is resulted. Ch.11 notes – P.2 These forces between fluctuating dipoles are often called ___________________ or _____________________. Fig 11-6 The greater the _________________________________ in a molecule, the instantaneous dipole can be set up more easily, and the van der Waals’ forces is _________________. Table 11-2 The van der Waals’ forces also increase with _____________________ of the molecule. e.g. 4. Magnitude of van der Waals’ forces: Table 11-1 C. Van der Waals’ radii 1. The ___________________ is one half of the distance between two atoms in the __________ molecule. 2. The _______________________ is one half of the distance between the nuclei of two atoms in _________________ molecules. Fig 11.9 Fig. 11-8 3. Since van der waals’ forces is much weaker than a covalent bond, the van der waals’ radius of a molecule is much _____________ than its covalent radius. Fig. 11-10 Ch.11 notes – P.3 D. Hydrogen bonding 1. Hydrogen bonding is a particularly _________________________________ interaction. When hydrogen is bonded to a __________________________ atom, the bonding electron pair is drawn towards the electronegative atom. As hydrogen has no inner shell electron and is very small in size, a _____________________________________________ is developed. The attraction between the ___________________electrons of the electronegative atom and the positively charged _______________________ of another molecule is called a hydrogen bond. Fig. 11-15 The strength of a hydrogen bond is about __________________ of a covalent bond. Table 11-3 The essential requirements for the formation of a hydrogen bond: a) A hydrogen atom usuallly bonded to a highly electronegative atom ___________________. b) An ________________________ electrons on the electronegative atom. 2. Hydrogen bonds in different cases: a) between same kind of molecules. b) between different kinds of molecules. c) within one molecules. Ch.11 notes – P.4 3. Experimental determination of the strength of the hydrogen bond: a) Hydrogen bonding is formed between trichloromethane and ethyl ethanoate. b) When these two liquids are mixed, a _____________________________ is observed. c) From the specific heat capacities and the quantities of reagents used, the enthalpy change that forms hydrogen bonds can be calculated. 4. Importance of hydrogen bonding in physical phenomena a) Anomalous properties of the second period hydrides Fig. 11-17 The abnormally ________________________________________________ of NH3, H2O and HF can be explained by the present of hydrogen bonds. b) Boiling points and solubilities of alcohol Fig. 11-18 The boiling points of alcohols are much __________ than the corresponding thiols. These can be explained by the present of hydrogen bonds between alcohol molecules. These can also explain why the lower alcohols can be _________________with water. c) Dimerization of carboxylic acids When the molar mass of carboxylic acid are found from measurements in the vapour phase, the values are up to ____________ the values calculated from the chemical formulae. This is because the molecules form ____________ through the formation of hydrogen bonds: Ch.11 notes – P.5 d) The different in boiling points between isomers Trans-butenedioic acid forms extensive ____________________ hydrogen bonds with neighbouring molecules; while cis-butenedioic acid forms _____________________ hydrogen bonding and forms less extensive intermolecular hydrogen bonds with neighbouring molecules. e) Different in hardness between anhydrous and hydrated salt Anhydrous magnesium sulphate solid is much ___________ than its hydrated form (MgSO4.7H2O), this is because in anhydrous form, the cations and anions are linked by _________________________; while in the hydrated form, water molecules are present between the ions and linked by hydrogen bonds only, hence the structure is much weaker. 5. Importance of hydrogen bonds in biochemistry a) Hydrogen bonding in water and ice In water, the molecules are in ___________________________, and the hydrogen bonds are formed and broken continually. In ice, molecules are ________________ in such a way that the maximum number of hydrogen bonds is formed. This results in a three-dimensional __________________________ structure which is an _________ structure. Fig. 11-21 This accounts for the fact that ice is _____________________ than water at 0oC. This fact makes ponds and lakes freeze from the surface downwards, and the layer of ice ___________________ the water below and prevents complete solidification, this allows aquatic lives to survive. Ch.11 notes – P.6 b) Hydrogen bonding in proteins The primary structure of a protein consists of a sequence of amino acids: Protein chains are held in _______________________ to one another by hydrogen bonds. This creates the _____________________ structure of protein. In many proteins, including those in hair, wool and nails, hydrogen bonding causes the protein chain to become _____________ into a tightly coiled ___________. Fig. 11-23 c) Hydrogen bonding in DNA DNA is present in the nuclei of living cells and carries ______________ ___________________. DNA consists of two macromolecular strands spiralling round each other in the form of a ____________________. Fig. 11-23, 11-24 The two nucleic acid chains are held together by _____________________. When a cell divides, the double helix of the DNA molecule ____________ by breaking down the hydrogen bonds. A ________________________ chain is formed adjacent to each of the original chain by the formation of new hydrogen bonds. Each of the newly formed double helix is received by each of the two cells. This gives an explanation of the ________________ of the DNA in every cell of an organism. Ch.11 notes – P.7 E. Phase diagrams of carbon dioxide and water A phase diagram is a graph showing the relationship between solid, liquid and vapour phase over a range of ________________ and ________________. A typical phase diagram: About the phase diagram: 1. Three curves appear, bounding the graph into 3 regions, each region represents the particular_______________ phase that is stable and can exist under those conditions. 2. Each point on the 3 curves represents the conditions under which ________________ phases of the substance ________________at _____________________. a) Line AT: __________________curve. Along the line, solid phase and liquid phase coexist at equilibrium. b) Line CT: ____________________curve. Along the line, liquid phase and vapour phase coexist at equilibrium. c) Line BT: __________________curve. Along the line, solid phase and vapour phase coexist at equilibrium. Ch.11 notes – P.8 3. Point T: _________________. This point represents the temperature and pressure at which the solid, liquid and vapour phases are in equilibrium. 4. Point C: _______________. At temperature higher than the critical temperature, the liquid phases become __________________________ from the vapour phase, and increasing the pressure cannot liquefy gas. Questions: On the phase diagram, state what happens, a) At constant temperature, the pressure is increased at point I? b) At constant temperature, the pressure is decreased at point II? c) At constant pressure, the temperature is increased at point II? d) At constant pressure, the temperature is decreased at point III? e) At point III, if the pressure is increased slightly, how could we maintain the equilibrium state of the system? f) At point T, if the temperature is increased slightly, is it possible to maintain the three phases equilibrium state? Ch.11 notes – P.9 Phase diagram of carbon dioxide: a) under 1 atm, and 25℃, carbon dioxide is in the _________________phase. b) Under 1 atm, when carbon dioxide is heated from -80℃ to 25℃, it changes from ___________phase to __________________phase, i.e. it ____________________. c) It is _____________________for carbon dioxide to exist as liquid at 1atm, however we could liquefy carbon dioxide at ____________________________. Ch.11 notes – P.10 Phase diagram of water: a) Under 1 atm, and 25℃, water is in the _______________________phase. b) Different from a typical phase diagram, the solid-liquid equilibrium line slant to the ____________________, i.e. at constant temperature, ____________________ pressure favors the melting of ice. This is the consequence of the pressure of __________________________in ice, which results in an __________________. An increase in pressure will cause the collapse of the structure and produce the water which is denser than ice. c) The dotted curve TD represents _______________ of water.