Download CH3511: PHYSICAL CHEMISTRY LAB I Lab 6

CH3511: PHYSICAL CHEMISTRY LAB I
Lab 6: Colligative Properties: Freezing Point Depression
PRELIMINARY REPORT
November 15, 2004
Section 1, Group 1
R. B. Student ([email protected])
T. Y. Student (tystudent)
M. G. Student ([email protected])
INTRODUCTION
In this experiment, the molar heat of fusion and the freezing point depression constant of
water will be calculated. The system being studied is an aqueous solution of varying
salts. Multiple systems containing different concentrations (ranging from 0.0179 m to
0.8961 m) of the salts magnesium chloride hexahydrate and calcium chloride dihydrate
will be observed. An Omega HH508 digital thermometer will be used to measure the
freezing points of each solution. From these freezing points, the freezing point
depression of each solution caused by colligative properties will be used to determine the
degree of dissociation of the salts in conjunction with the provided sucrose data [1].
THEORY
Whenever a pure substance undergoes a phase change at constant temperature (for
instance from liquid to solid), equilibrium is reached between the two phases such that
the chemical potentials of the two phases are equal, satisfying equation (1).
µ A( s ) * = µ A( l ) *
(1)
Where µA(s)* is the chemical potential of pure substance A in the solid phase and µA(l)* is
the chemical potential of pure substance A in the liquid phase. Since the chemical
potentials of the two phases are only equal at one temperature (for a specified pressure), it
can be concluded that chemical potential is a function of temperature. For equation (1)
relating the liquid and solid phases, the specific temperature is called the freezing
temperature, Tf. When a solute is added to the liquid phase, forming a solution with A as
the solvent, the chemical potential of A in the solution is usually lower than the chemical
potential of pure liquid A. This expression is displayed in expression (exp1).
µ A( s ln) < µ A(l ) *
(exp1)
Where µA(sln) is the chemical potential of substance A in the solution. With the reduced
*
chemical potential of the non-solid phase, the temperature at which µ A( s ) = µ A( s ln) is
reduced, exhibiting a freezing point depression in the solution. Equation (2) relates the
chemical potential of substance A in solution to the chemical potential of pure substance
A (as a liquid) for all solutions.
µ A( s ln) = µ A(l ) * + R ⋅ T ⋅ ln (Α A )
(2)
Where R is the gas constant, T is the absolute temperature, and ΑA is the activity of
*
substance A in solution. At the freezing temperature, µ A( s ) = µ A( s ln) , transforming
equation (2) into equation (3).
2
µ A( s ) * = µ A(l ) * + R ⋅ T f ⋅ ln (Α A )
(3)
Rearranging equation (3) produces equation (4).
ln (Α A ) =
µ A( s ) * − µ A( l ) *
(4)
R ⋅Tf
Using the definition of chemical potentials, it can be observed that the chemical potential
of a pure substance (a single phase) is equal to the molar Gibbs energy of that substance.
This relation is described in equation (5).
 ∂G 
*
 = Gm, A
∂
n

T ,P
µ A* ≡ 
(5)
Where G is Gibbs energy, n is moles, P is pressure, and Gm,A* is the molar Gibbs energy
of pure substance A. Applying equation (5) to equation (4) twice produces equation (6).
ln (Α A ) =
*
G m , A( s ) − G m , A( l )
*
(6)
R ⋅Tf
Where Gm,A(s)* is the molar Gibbs energy of pure substance A in the solid phase and
Gm,A(l)* is the molar Gibbs energy of pure substance A in the liquid phase. The molar
change in Gibbs energy for fusion of substance A is then defined in equation (7).
*
∆ fus Gm , A ≡ Gm , A(l ) − Gm , A( s )
*
(7)
Where ∆ fus Gm , A is the molar change in Gibbs energy for fusion of substance A. Applying
equation (7) to equation (6) produces equation (8).
ln (Α A ) =
− ∆ fus Gm , A
R ⋅Tf
(8)
The definition of activity is then presented in equation (9).
Α A = γ A ⋅ xA
(9)
Where γA is the mole-fraction-adjusted activity coefficient of substance A and xA is the
mole fraction of substance A in the solution. Applying this definition to equation (8)
produces equation (10).
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ln (γ A ⋅ x A ) =
− ∆ fus Gm, A
(10)
R ⋅Tf
For dilute solutions under ideal conditions, γA is equal to 1 and equation (10) simplifies to
equation (11).
ln ( x A ) =
− ∆ fus Gm, A
(11)
R ⋅Tf
Differentiating equation (11) with respect to Tf produces equation (12).
 − ∆ fus Gm , A 

d
 R ⋅T

d (ln( x A ))
f

= 
dT f
dT f
(12)
Using an applied form of the results from the discussion on pages 182-183 of Levine [2],
equation (13) can be produced.
 − ∆ fus Gm , A 

d
 R ⋅T
 ∆ H
f

 = fus m , A
2
dT f
R ⋅Tf
(13)
Where ∆ fus H m, A is the molar heat of fusion of substance A. Substituting equation (13)
into equation (12) produces equation (14).
d (ln ( x A )) =
∆ fus H m , A
R ⋅Tf
2
⋅ dT f
(14)
Using mathematical formulas for differentiation, equation (14) can become equation (15).
d (ln ( x A )) =
− ∆ fus H m , A
R
 1
⋅ d
T
 f




(15)
By equation (15), the slope of ln(xA) with respect to (1/Tf) is directly proportional to the
molar heat of fusion of substance A, allowing the molar heat of fusion of substance A to
be directly calculated from the slope of the plot.
The integration of equation (14) from a state of pure substance A (xA = 1 and Tf = Tnfp, the
normal freezing point) to another state (0 < xA < 1) produces equation (16). For this
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integration, it was assumed that the molar heat of fusion of substance A was constant with
respect to temperature/freezing temperature.
xA
Tf
1
Tnfp
∫ d (ln(xˆ A )) =
∫
ln ( x A ) − ln(1) =
ln ( x A ) =
∆ fus H m , A
⋅ dTˆ f ⇒
2
R ⋅ Tˆ
f
∆ fus H m, A  1
1 
⋅
− ⇒
T

R
 nfp T f 
∆ fus H m , A  T f − Tnfp
⋅
 T ⋅T
R
 f nfp
(16)




Where x̂ A and Tˆ f are dummy variables for integration. It should be noted that Tfpd is the
same as the freezing point of pure substance A, Tf*. The change in freezing temperature
caused by the addition of solute, ∆Tfpd, can be defined by equation (17).
∆T fpd ≡ T f − Tnfp
(17)
If it is assumed that ∆Tfpd is small, that is, Tf ≈ Tnfp, equation (16) can be simplified to
equation (18). This simplification also applies equation (17).
ln ( x A ) =
∆ fus H m , A  ∆T fpd
⋅
T 2
R
 nfp




(18)
In the derivation of equation (18), it was assumed that the solution was ideal in order to
simplify the activity expression. If it is further assumed that the solution is dilute,
equation (19) will hold.
ln ( x A ) = − x B
(19)
Where xB is the mole fraction of the solute (substance B) in the solution. The definition
of mole fraction is then displayed in equation (20).
xB =
nB
n A + nB
(20)
Where nB is the number of moles of substance B in solution and nA is the number of
moles of substance A in solution. In a dilute solution where substance A is the solvent,
equation (20) can be simplified to equation (21).
xB =
nB
nA
(21)
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The definition of molality is displayed as equation (22).
m=
nB
mA
(22)
Where m is the concentration of the solution (molality) and mA is the mass of substance A
(solvent) in the solution. Recognizing that mA = nA * MWA (where MWA is the molecular
weight of substance A), equation (22) can be reduced to equation (23).
m=
nB
x
= B
n A ⋅ MW A MW A
(23)
Substituting equation (23) into equation (19) and then into equation (18) produces
equation (24).
− m ⋅ MW A =
∆ fus H m , A  ∆T fpd
⋅
T 2
R
 nfp




(24)
Solving equation (24) for ∆Tfpd produces equation (25).
∆T fpd =
− MW A ⋅ R ⋅ Tnfp
2
∆ fus H m , A
⋅m
(25)
In the derivation of equation (25), several assumptions about the solution were made. It
was assumed that the solution is at constant pressure, the molar heat of fusion of
substance A is constant with respect to temperature, the solution is ideal, the solution is
dilute, and that ∆Tfpd is sufficiently small.
The molal freezing-point depression constant, Kf, is then defined by equation (26).
Kf =
MW A ⋅ R ⋅ Tnfp
2
∆ fus H m , A
(26)
Substituting equation (26) into equation (25) produces equation (27).
∆T fpd = − K f ⋅ m
(27)
Colligative properties have been shown in previous experiments to be dependent on the
number of species in the solution, not solely on the concentration of the solute in the
solution [1]. However, for a solution with a non-electrolytic solute, equation (27) still
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holds. For this reason, the van’t Hoff factor, i, is used to account for the increased
colligative properties of electrolytes. The van’t Hoff is defined in equation (28).
i=
∆T fpd
(∆T )
(28)
fpd 0
Where ∆Tfpd is the freezing point depression of a solution with electrolytes and (∆Tfpd)0 is
the freezing point depression of a solution with a non-electrolytic solute at the same
concentration. As the concentration (molality) of the solution decreases, the van’t Hoff
factor approaches the number of species in solution (1 for non-electrolytes like sucrose, 2
for 2-species electrolytes like sodium chloride, 3 for 3-species electrolytes like
magnesium chloride, etc.).
Since the colligative properties of a non-electrolytic solute can be described by equation
(27), equation (29) must hold.
(∆T )
fpd 0
= −K f ⋅ m
(29)
Substituting equation (29) into equation (28) and rearranging produces equation (30).
∆T fpd = −i ⋅ K f ⋅ m
(30)
Equation (30) then accounts for the freezing point depression of solutions of both
electrolytes and non-electrolytes.
The laboratory information sheet provided on the CH3511 website [1] and the textbook
Physical Chemistry by Ira Levine [2] were used heavily in the preparation of this
analysis.
PRE-LABORATORY EXERCISES
1. The requested information was included in the theory section of the report.
2. Using the CRC Handbook of Chemistry & Physics, 1996-1997 edition [3], the
literature values for the Kf of water and the molar heat of fusion of water. The Kf
value was found to be 1.86 K-kg/mol and the molar heat of fusion was found to be
6.01 kJ/mol at the normal freezing point of water (Tnfp = 0.00°C).
3. The requested information was included in the procedure section of the report.
4. The normal freezing point of ethanol was obtained from the CRC Handbook of
Chemistry & Physics [3] and found to be -114.1°C at 0.1 MPa (roughly atmospheric
pressure).
The freezing point depression of the solution of methanol in ethanol was then
calculated using this normal freezing point of ethanol and equation (17).
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∆T fpd ≡ T f − Tnfp
= -115.3°C – (-114.1°C)
= -1.2°C
This freezing point depression represents the (∆Tfpd)0 since methanol is not an
electrolyte.
Using equation (17), the freezing point depression of the KCl in ethanol solution was
also calculated to be -2.0°C. This freezing point depression represents a ∆Tfpd since
KCl is an electrolyte.
Lastly, the van’t Hoff factor for KCl in ethanol was calculated using the freezing
point depressions of the two solutions and equation (28). Equation (28) was only able
to be used since the two solutions had the same concentration (1 molal).
i=
∆T fpd
(∆T )
fpd 0
= -2.0°C / -1.2°C
= 1.67
The calculated van’t Hoff factor for KCl in ethanol is not the expected value. Since
two dissociated species are produced when KCl is dissolved in solution, the expected
van’t Hoff factor for KCl would be 2. According to the laboratory protocol [2], the
van’t Hoff factor is only equal to the “expected” value for decreasingly lower
concentrations (small molalities), as described in equation (1e).
lim i = iexp ected
m →0
(1e)
At higher concentrations, the van’t Hoff factor is lower than the expected value, as
observed with the data for this question—1 molal solutions are sufficiently
concentrated for the van’t Hoff factor to differ from the expected value.
EXPERIMENTAL PROCEDURE
I.
II.
Equipment Setup
A. Place 25mL of distilled water into a test tube.
B. Place the thermometer probe with the metal stirrer around it into the test tube.
1. Make sure that the thermometer probe is attached to an Omega
HH508 digital thermometer.
C. Fill the Dewar with liquid nitrogen.
D. Layer a large beaker with equal amounts of non-reagent-grade salt and ice.
Calibration
A. Attach the test tube to a ring stand with a clamp.
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III.
B. Slowly lower the test tube into the Dewar until the water in the test tube is
submerged in the liquid nitrogen.
C. Use the metal stirrer to stir the water.
D. Remove the test tube when the water is close to freezing and place it in the
ice/salt/water bath until it freezes in order to slow the freezing process and
obtain a more accurate reading.
1. Continue stirring while the test tube is in the ice/salt/water bath.
E. When solid ice is present and the temperature remains constant, record the
temperature from the digital thermometer.
1. This temperature is the freezing point.
2. Do not use the lower temperature produced by super cooling.
F. After the water is significantly slushy, place the test tube in a beaker of warm
water until all the slush is melted.
G. Cool the water again using the same procedure to obtain more freezing
temperatures.
1. Repeat this process enough times to determine the freezing point of
water.
Collection of Freezing Point Depression Data
A. Prepare 12 solutions of roughly 35mL of MgCl2·6H2O and CaCl2·2H2O
1. Prepare the solutions using the mass of water to obtain concentration
in molalities.
2. The freezing point depressions should range from 0.1 to 1K, ~2.5K,
and ~5K (in absolute value). Solubility may limit the freezing point
depressions to less than 5 degrees.
A sample calculation using equation (30) is given for a freezing
point depression of 0.1 K in an aqueous solution of magnesium
chloride hexahydrate (i = 3, ideally). The literature value of 1.86 Kkg/mol was used for the Kf of water. By definition, ∆Tfpd is negative,
so the value -0.1 K is used.
∆T fpd = −i ⋅ K f ⋅ m ⇒
m=
− ∆T fpd
i⋅Kf
= – -0.1 K / (3 * 1.86 K-kg/mol)
= 0.0179 m
Using the definition of molality, the amount of solute can be
calculated using equation (1p) as described in the next sample
calculation (for magnesium chloride hexahydrate). For this
calculation, it is assumed that the mass of the solution is 35 g and
that the entire mass of the solution comes from the water solvent (for
dilute solutions, the mass of solute is negligible).
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m=
n solute
mass solute
=
⇒
mass solvent MWsokute ⋅ mass solvent
(1p)
mass solute = m ⋅ MWsolute ⋅ mass solvent
= 0.0179 m * 203.29 g/mol * 35 g
= 0.128 g
In a similar fashion, the mass of calcium chloride dihydrate can be
calculated using the formula weight of calcium chloride dihydrate
instead of the formula weight of magnesium chloride hexahydrate.
Table I displays the desired freezing point depression (in absolute
value), the corresponding solution concentration (in molality), and
the amounts of magnesium chloride hexahydrate and calcium
chloride dihydrate needed to make the solutions.
Table I: Masses of MgCl2·6H2O and CaCl2·2H2O Needed for the Desired Solutions
∆Tf (K)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
2.5
5.0
m (molal) mass MgCl2·6 H20 (g) mass CaCl2·2 H20 (g)
0.0179
0.128
0.092
0.0358
0.255
0.184
0.0538
0.383
0.277
0.0717
0.510
0.369
0.0896
0.638
0.461
0.1075
0.765
0.553
0.1254
0.893
0.645
0.1434
1.020
0.738
0.1613
1.148
0.830
0.1792
1.275
0.922
0.4480
3.188
2.305
0.8961
6.376
4.611
B. Determine the freezing point of each solution using the procedure described
above for determining the freezing point of water.
C. Calculate the freezing point depression of each solution using equation (17).
∆T fpd ≡ T f − Tnfp
= -1.5°C – 0.0°C
= -1.5 K
IV.
For an aqueous solution with a freezing point of -1.5°C.
Data Analysis
A. Correct molality concentrations so that the mass of solvent includes the water
from the hydrated salts. This can be accomplished using equation (2p).
mass water ,corrected = mass water +
mass solute
⋅ hydrate ⋅ MWwater
MWsolute
(2p)
10
= 35.0000 g + 0.6579 g / (203.29 g/mol) * 6 * 18.01 g/mol
= 35.3497 g
Where masswater,corrected is the corrected mass of water in the solution
hydrate is the number of water molecules associated with each formula
unit of the salt (6 for magnesium chloride hexahydrate).
MWwater is the molecular weight of water
B. Construct a plot of ∆Tfpd versus m to determine the molal freezing point
depression constant for water, which can be calculated from the slope of the
plot using the differential of equation (30) with respect to m and the ideal
van’t Hoff factor for the solute. This relationship is described in equation
(3p).
∆T fpd = −i ⋅ K f ⋅ m ⇒
d (∆T fpd )
dm
= −i ⋅ K f ⇒
(3p)
 d (∆T fpd ) 


dm 

Kf =
−i
= -4.76 K-kg/mol / -3
= 1.59 k-kg/mol
C. Calculate the van’t Hoff factor for the two electrolytes using the measured
data the sucrose data provided from the CH3511 website [1], and equation
(28).
i=
∆T fpd
(∆T )
fpd 0
= -1.50 K / -0.51 K
= 2.94
D. Construct a plot of ln(xA) vs. 1/Tf to determine the molar heat of fusion for
water. xA is the mole fraction of water in each solution. The molar heat of
fusion of water can be calculated from a rearranged form of equation (15).
d (ln ( x A )) =
− ∆ fus H m , A
∆ fus H m , A = − R ⋅
R
 1
⋅ d
T
 f
d (ln ( x A ))
d (1 T f )

⇒


= - 8.3145 J/(mol-K) * -7195 K
= 59.8 kJ/mol
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The slopes of the plots used in the calculations of steps B and D can be
obtained from the linear regression of the appropriate data sets.
SAFETY
Information concerning the safety of all reagents used in a laboratory is crucial in the
event of unforeseen problems. For this reason, safety guidelines for all used reagents
were compiled in Tables II, III, IV, V, VI, and VII. General laboratory safety procedures
like wearing eye protection and gloves (when needed) were followed in addition to the
safety guidelines outlined in these tables.
Table II: Safety Guidelines for Sucrose [4]
Description
Physical Constants
Acute Chemical
Hazards
Disposal
First Aid
Fire Extinguishing
Spills
white or colorless solid
MW 342.29 gram/mole
BP N/A
MP 185.0˚C
eye irritation, skin irritation, respiratory tract irritation,
gastrointestinal tract irritation, and digestive tract irritation
dispose of in a designated disposal container
skin: flush with plenty of water for 15 min.
eyes: flush with plenty of water for 15 min.
inhalation: remove to uncontaminated area, seek medical attention
ingestion: if alert and conscious, give 2-4 cupfuls of milk
water spray, dry chemical, carbon dioxide, or appropriate foam
sweep up or vacuum material, place in a disposal container
Table III: Safety Guidelines for Sodium Chloride [5]
Description
Physical Constants
Acute Chemical
Hazards
Disposal
First Aid
Fire Extinguishing
Spills
white or colorless solid
MW 58.43 gram/mole
BP 1412.6˚C
MP 801.0˚C
eye irritation, skin irritation, respiratory tract irritation, nausea,
vomiting, gastrointestinal tract irritation, rigidity, and convulsions
dispose of in a designated disposal container
skin: flush with plenty of water for 15 min.
eyes: flush with plenty of water for 15 min.
inhalation: remove to uncontaminated area, seek medical attention
ingestion: if alert and conscious, give 2-4 cupfuls of milk
water spray, dry chemical, carbon dioxide, or chemical foam
sweep up or vacuum material, place in a disposal container
12
Note: non-reagent-grade sodium chloride is used in this experiment. The safety
guidelines outlined above should still be followed.
Table IV: Safety Guidelines for Magnesium Chloride Hexahydrate [6]
Description
Physical Constants
Acute Chemical
Hazards
Disposal
First Aid
Fire Extinguishing
Spills
white to gray-white solid
MW 203.2914 gram/mole
BP 1412˚C
MP 118˚C
eye irritation, skin irritation, digestive tract irritation, respiratory
tract irritation, nausea, vomiting, diarrhea, and metal fume fever
(metallic taste, fever, chills, cough, weakness, chest pain, muscle
pain, and increased white blood cell count)
dispose of in a clean, dry disposal container
skin: flush with plenty of water for 15 min.
eyes: flush with plenty of water for 15 min.
inhalation: remove to uncontaminated area, seek medical
attention, do not attempt mouth to mouth resuscitation
material will not burn
sweep up of absorb material, place in a clean, dry disposal
container
Table V: Safety Guidelines for Calcium Chloride Dihydrate [7]
Description
Physical Constants
Acute Chemical
Hazards
Disposal
First Aid
Fire Extinguishing
Spills
white, odorless solid
MW 147.0128 gram/mole
BP 1599.8˚C
MP 259.9˚C
eye irritation, skin irritation, gastrointestinal tract irritation,
respiratory tract irritation, nausea, vomiting, seizures, rapid
respiration, slow heartbeat, cardiac disturbances, and burns
dispose of in a clean, dry disposal container
skin: flush with plenty of water for 15 min.
eyes: flush with plenty of water for 15 min.
ingestion: if alert and conscious, give 2-4 cupfuls of milk
inhalation: remove to uncontaminated area, seek medical
attention, do not attempt mouth to mouth resuscitation
material will not burn
sweep up or vacuum material, place in clean, dry disposal
container
Table VI: Safety Guidelines for Liquid Nitrogen [8]
Description
Physical Constants
colorless, odorless, cryogenic liquid
MW 28.01 gram/mole
BP -195.8˚C
13
Acute Chemical
Hazards
Disposal
First Aid
Fire Extinguishing
Spills
MP -209.9˚C
dizziness, drowsiness, nausea, vomiting, excess salivation,
diminished mental alertness, loss of consciousness, tissue
freezing, severe burns, blisters
do not attempt to dispose of unused product, return excess and
container to supplier
skin: warm frostbit area with warm water, seek medical attention
eyes: warm frostbit area with warm water, seek medical attention
inhalation: remove to uncontaminated area
nonflammable
evacuate area immediately and monitor oxygen level
Table VII: Safety Guidelines for Water [9]
Description
Physical Constants
Acute Chemical
Hazards
Disposal
First Aid
Fire Extinguishing
Spills
colorless, odorless liquid
MW 18.0134 gram/mole
BP 100°C
non-hazardous
Sink
skin: no treatment
eyes: no treatment
ingestion: no treatment
inhalation: no treatment
liquid will no burn
absorb with inert material and put in container
REFERENCES
1. Smith, Kelley, “Physical Chemistry Lab”.
<http://www.chemistry.mtu.edu/~kmsmith/PChem>. 14 Sep. 2004.
2. Levine, Ira N. Physical Chemistry, Fifth Edition, McGraw-Hill, New York,
2002, pp. 342-346.
3. Lide, David R. (ed.), et al. Handbook of Chemistry and Physics. The Chemical
Rubber Company, Cleveland, OH, 1997, pp. 6-10, 6-53, 6-128, 6-131, 15-21.
4. “MSDS: Sucrose”. <https://fscimage.fishersci.com/msds/96540.htm>. 14 Nov.
2004.
5. “MSDS: Sodium Chloride” <https://fscimage.fishersci.com/msds/21105.htm>.
14 Nov. 2004.
6. “MSDS: Magnesium Chloride Hexahydrate”.
<https://fscimage.fishersci.com/msds/13365.htm>. 14 Nov. 2004.
7. “MSDS: Calcium Chloride Dihydrate”.
<https://fscimage.fishersci.com/msds/03901.htm>. 14 Nov. 2004.
14
8. “MSDS: Liquid Nitrogen”.
<http://www.medicine.uiowa.edu/biochemstores/Pages/ln2msds.htm>. 14 Nov.
2004.
9. “MSDS: Water”. <http://www.chemistry.mtu.edu/~djchesne/classes/ch2212/>.
31 Aug. 2004.
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