CHE2612/201/1/2011

DEPARTMENT OF CHEMISTRY

PHYSICAL CHEMISTRY

MODULE CHE2612

TUTORIAL LETTER 201 : 2011

CONTENTS

1.

Key to Assignment 01

Mr M.E. Aphane Tel no (012) 429 8028 E-mail: aphanme@unisa.ac.za

2 At this stage you should have received the following study material for CHE2612:

1.

Study Guide

Only Guide for CHE2612

2.

CHE2612/101/3/2011

Regulations, procedures, advice and assignments October/November 2010 Exam Paper

3.

CHE2612/102/3/2011

If you have not received all this tutorial matter please approach the Call Centre at telephone no.: 086 167 0411.

CHE2612/201/1

KEY TO ASSIGNMENT 1
Question 1

(a) The equation of state is an equation that interrelates the variables / properties such as pressure, p, volume, V, number of moles, n, and temperature, T, which describes the physical state of a gas, and has a general formula:

P = f(T, V, n)

Two examples are: Perfect gas equation of state, PV = nRT

nRT an 2 - 2 V nb V

and van der Waals equation of state: P =

(b) Deviations of real gases from ideal gases in terms of compression factor, Z, The compression factor, Z, of a gas is the ratio of its measured molar volume, Vm = V/n, to the molar
o volume of a perfect gas, Vm at the same pressure and temperature, and is given by:

pVm RT

Because for a perfect gas Z = 1 under all conditions, deviations of Z from 1 is a measure of departure from perfect behaviour. At very low pressures, all the gases have Z 1, and behave nearly perfectly. At high pressure, the gases have Z > 1, and have larger molar volumes than a perfect gas, repulsive forces are dominant. At intermediate pressures, most gases have Z < 1, indicating that attractive forces are dominant, and have smaller molar volume than a perfect gas.

Deviations of real gases from ideal gases in terms of Critical constants Consider a liquid which is heated in a rigid, closed vessel. The vapour pressure, and hence the density of the vapour rise as the temperature is raised. At the same time, the density of liquid decreases slightly as result of its expansion. Then there comes a stage when the density of the vapour equals that of the remaining liquid, and the surface separating the two phases disappears. The temperature at which the

4 surface disappears is called the critical temperature, Tc, of the substance, and the vapour pressure at the critical temperature is called the critical pressure, pc. Consider Figure 1.15 in Atkins, an isotherm slightly below Tc and at a certain pressure, a liquid condenses from the gas and is distinguishable from it by the presence of a visible surface. If, however, the compression takes place at Tc itself (i.e, in the vapour phase), then a surface separating two phases does not appear and the volumes at each end on the horizontal part of the isotherm have merged to a single point called the critical point of the gas. The temperature, pressure and the volume at that critical point are called critical temperature, Tc, critical pressure, pc, and critical volume, Vc, of that substance, and collectively pc, Tc, Vc are called critical constants. The critical constants represent the state of a system at which the distinction between the liquid and the vapour phase (gas) disappears. Above the critical temperature, the liquid phase cannot be produced by the application of pressure alone (above the critical temperature, the liquid phase of a substance does not exist). At and above Tc, the sample has a single phase that occupies the entire volume of the container that gas so called fluid is called supercritical fluid.

Question 2
Option 1: The partial pressure, PJ, of a gas component J in a mixture of gases is defined as: PJ = XJP XJ = mole fraction of gas component J P = total pressure of the gaseous mixture then, PH2O = XH2O x Ptot
PH 2 O 24 Torr = Ptot 75 Torr

XH 2O =

= 0.032 Note also that, XA + XB + = 1 XN2 = 1 XH2O = 0.968 = 1 0.032

5 And PN2 = XN2 x Ptot = 0.968 x 750 Torr = 726 Torr

CHE2612/201/1

From the ideal gas law (Perfect gas law, PV = nRT), we calculate the number of moles of N2 as follows:

N2

PN2 V (726/760) atm x 0.45 L = RT 0.08206 L atm K -1 mol -1 x 298 K

= 0.01758 mol mass of N2 collected is : = nN2 x Molar mass of N2 = 0.01758 mol x 28.02 g.mol-1 = 0.493 g

Option 2: According to Daltons law: Ptot = PH2O + PN2 PN2 = Ptot - PH2O = (750 24) Torr = 726 Torr From the ideal gas law (Perfect gas law, PV = nRT), we calculate the number of moles of N2 as follows:

N2

PN2 V (726/760) atm x 0.45 L = RT 0.08206 L atm K -1 mol -1 x 298 K

= 0.01758 mol mass of N2 collected is : = nN2 x Molar mass of N2 = 0.01758 mol x 28.02 g.mol-1 = 0.493 g

Question 3 (a) Using an ideal gas law, the initial pressure of N2O4 in a 500 cm3 volume at 25oC (298 K) is: P=
nRT 1.588 g =( V 92.01g.mol = 0.855 bar
1

)x

8.314 x 10 -2 L bar K -1 mol -1 x 298 K 0.500 L

6 From first year General Chemistry, the equilibrium table is set as follwos: N2O4 (g) 0.855 -x 0.855 - x 2NO2 (g) 0 +2x 2x

Initial (bar) Change Equilibrium

Using Daltons law: PN2O4 + PN02 = Ptot i.e, (0.855 x) + 2x = 1.033 bar x = (1.033 0.855) bar = 0.178 bar At equilibrium, the amounts (in bar) are: PN2O4 = 0.855 x = 0.677 bar PNO2 = 2x = 0.356 bar

And mole fractions are calculated as follows: XN2O4 =

XNO2 =

(b) The percentage N2O4 (g) dissociated is: % Dissociated = =

= = 20.8 %

7 Question 4 (a) By considering only the first three terms of the Virial equation of state, the expression becomes:

CHE2612/201/1

PVm = RT [1+ i.e P

C B + ] 2 Vm Vm C RT B = [1+ + ] 2 Vm Vm Vm

= RT [

B C 1 + + ] 2 3 Vm Vm Vm 3C Vm
4

So that

P Vm

= RT [
T

1 Vm
2

2B Vm
3

RT Vm
2

2 BRT Vm

3CRT Vm
4

And

P T

=R[
Vm

B C 1 + + ] 2 3 Vm Vm Vm

= (b)

BR CR R + + 2 3 Vm Vm Vm

P Vm T

Vm

P T

BR R CR + + 2 3 Vm Vm Vm Vm R 2 BR 3CR = 2 3 4 Vm Vm Vm
= And

P T Vm

P Vm
RT

= =

Vm
2

2 BRT Vm Vm
2
3

3CRT Vm
4

R Vm

2 BR Vm
3

3CR
4

Which proves that:

P Vm T

P T Vm

8 Question 5 (a) The molar volume (Vm) of N2 (g) using the perfect gas law is calculated as follows: PV = nRT Or
V RT = Vm = P n 8.314 x 10 -2 L bar K -1 mol -1 x 500 K = 500 bar = 0.08314 L . mol-1

(b) The third Virial coefficient, C, is usually less important than the second coefficient, B, in the sense that at typical molar volumes, C/V2m <<B /Vm

The virial equation of state then becomes: PVm = RT 1 + i.e, Vm = =

B Vm

B RT 1+ P Vm

RT BRT + P PVm RTVm BRT 2 Vm = + P P RTVm BRT 2 Vm =0 P P 2 Vm - 0.08314 L . mol-1 Vm 0.00141 L2 . mol-2 = 0

We solve the last equation using quadratic equation:

i.e, Vm = =

0.08314 L. mol -1

0.08314 L. mol -1 2 -1 Vm = 0.0976 L. mol or Vm = -0.0144 L. mol-1

equation.

(-0.08314 L. mol -1 ) 2 - 4(1)(-0.00141 L2 . mol -2 ) 2 -1 0.112 L. mol

But the molar Volume cannot be negative, so Vm = 0.0976 L. mol-1for N2 (g) according to the virial

9 Question 6

CHE2612/201/1

(a) The compression factor, Z, of a gas, is the ratio of its measured molar volume, Vm (Vm =
V ), to the molar volume of a perfect gas at the same pressure and n

temperature, and is given by: Z= (b) Since Z =

PV m RT

PV m a RT , and the van der Waals equation of state is P = RT Vm b V m 2

Z=P Z=

Vm RT

= -

RT Vm b

a Vm
2

Vm RT

Vm Vm b

a Vm RT

The condition for which Z < 1, are such that:

a < 1 Vm b Vm RT Vm (Vm RT) - a(Vm b) <1 (Vm - b)(Vm RT)

Z<1

Vm

Vm RT - aVm
2

ab

Vm RT - bVm RT
2

<1
2

Vm RT aVm + ab < Vm RT - bVmRT aVm + ab + bVmRT < 0 Vm(bRT - a) + ab < 0

This expression can only be negative (i,e < 0) only if (bRT - a) < 0, since the molar volume and also ab (van der Waals parameters) are always positive.

bRT < a b<

a , RT

Z < 1 when b <

a , i.e when attractive forces dominate. RT

In a similar way: Vm(bRT - a) + ab >0

As above, (bRT - a) > 0, because Vm and ab are always positive bRT > a b>
a , RT

Z >1 when b >

a , i.e when repulsive forces dominate. RT

10 Question 7 (a) The perfect gas law is given by: PV = nRT P =

nRT 10.0 mol x 0.008206 L. atm. K -1 mol -1 x 300 K = V 4.860 L = 50.6 atm

(b) The van der Waals equation of state is:

RT Vm b

P= And

a Vm
2

V 4.860 L = Vm = = 0.486 L . mol-1 10.0mol n

From Table 1.6 (Atkins), the van der Waals coefficients for C2H6 (g) are a = 5.507 atm L2. mol-2 and b = 6.51 x 10-2 L .mol-1
5.507 L2 . mol -2 0.08206 L. atm. K -1 mol -1 x 300 K 2 0.486 L. mol -1 - 0.0651 L. mol -1 0.486 L. mol - 1 = 58.48 atm - 23.33 atm

P=

= 35.15 atm

Question 8

(a) The work done for expansion work, when the volume changes from Vi to Vf is given by:

w=-

Vf Vi

Pex dV

but since the gas is expanded irreversibly and isothermally against a constant opposing external pressure, Pex, the constant Pex is taken outside the intergral: i.e, w = - Pex
Vf Vi

dV

= - Pex (Vf Vi) Isothermal means Ti = Tf = T w = - Pex (Vf Vi)

11 = - Pex nRT Pf = nRT

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nRT [perfect gas] Pi

.Pex = Pf = 100 kPa
100 kPa 100 kPa

Pex Pex Pf Pi

100 kPa = 10.0 mol x 8.314 J K-1 mol-1 x 300 K x 200 kPa = - 12.5 x 103 J

= -12.5 kJ (b) The expansion work executed isothermally and reversibly is given by:

w = -nRT In

Vf Vi Vf Vi
=
Pi Pf

but for a perfect gas and Boyles law,

Pi Pf

w = -nRT In

200 kPa = -10.0 mol x 8.314 J K-1 mol-1 x 300 K In 100 kPa = -17.3 x 103 J = -17.3 kJ

(c) The work done by a perfect gas when it expands reversibly and isothermally is equal to the Area under the isotherm P = nRT / V, from the initial value (Pi, Vi) to the final values (Pf, Vf) at constant Temperature as shown in the figure below. This is consistent with Boyles law that the higher the volume, the lower the pressure (P = 1/V) at constant Temperature.

12

Pi

(Pi, Vi)

Area = Wrev = Pressure, P

Pf

(Pf, Vf)

Vi

Volume, V

Vf

The work done during an irreversible isothermal expansion against a constant external pressure equal to the final pressure of the gas is equal to the Area = Pex (V) = Wirr, a shaded area in the figure below, from values (Pex = Pf, Vi) to (Pex = Pf, Vf)

Pi

Area = Wirr = Pex (V) Pressure, P

Pex = Pf

(Pf, Vf)

Vi

Volume, V

Vf

13 Question 9 The standard reaction enthalpy (rH) for the reaction:

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1 1 H2 (g) + Br2 (g) HBr (g) 2 2 is calculated as follows using Hees law. This reaction can be recreated from the

given reaction equations as follows:

1 1 H2 (g) + Br2 (l) 2 2 Br2 (l)

HBr (g) Br2 (g)

rH = -36.23 kJ rH = 30.71 kJ

By reversing the second reaction equation from above equations and multiplying by 1/2 gives:
1 1 H2 (g) + Br2 (l) HBr (g) rH = -36.23 kJ 2 2 1 1 1 Br2 (g) Br2 (l) rH = (- x 30.71 kJ) 2 2 2 1 1 1 Overall: H2 (g) + Br2 (g) HBr (g) rH = -36.23 kJ + (- x 30.71 kJ) 2 2 2 rH = -51.58 kJ i.e, the standard reaction enthalpy of the above reaction at 298 K is = -51.58 kJ. mol-1

According to Kirchhoffs law (equation 2.36 Atkins): rH (1000 K) = rH (298 K) +

1000 25 r

C p dT

Assuming that the heat capacity of all substances participating in a given chemical reaction are constant over the temperature range involved, the Kirchhoffs law integrates to: rH (1000 K) = rH (298 K) + r C p (T2 T1) Where r C p is the difference of the heat capacities of products and reactants under standard conditions, i,e, r C p =

rC p ,m reactants 1 1 = Cp,m (HBr) C p,m (H2) + Cp,m (Br2) 2 2

rC p ,m products

14 = 29.142 J K-1 mol-1 { = -3.28 J K-1 mol-1 = -0.00382 kJ K-1 mol-1

1 (28.82 J K-1 2

mol-1) + (36.02 J K-1 mol-1) }

The r C p , m values are taken from Table 2.5 from data section of Atkins. It then follows that: rH (1000 K) = -51.58 kJ. mol-1 + (1000 K 298 K) x -0.00382 kJ K-1 mol-1 = -51.58 kJ. mol-1 + (702K) (-0.00382 kJ K-1 mol-1) = -54.26 kJ. mol-1

Question 10 A device for measuring the change in internal energy, U, is called a constant volume bomb calorimeter. Thus, a change in internal energy can be indentified with the heat supplied at constant volume (i,e, U = qv, since w = 0). The internal energy for Benzoic acid is given, and since the experiment for combustion of D-ribose is performed in the same calorimeter, the heat capacity will be the same. Then U = qv = CvT Cv = heat capacity at constant volume This heat capacity can be determined from the combustion of Benzoic acid, for which U = -3251 kJ.mol1

U = qv =

0.825 g 122.12 g.mol = -21.96 kJ

qv T

x (-3251 kJ.mol-1)

Cv =

21.96 kJ = 11.32 kJ.K-1 1.940 K

15 The internal energy for D-ribose is: U = - CvT = - (11.32 kJ.K-1) x 0.910 K x = -2127 kJ.mol-1

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150.13g.mol 0.727 g

Equation 2.21 (Atkins) states that the change in enthalpy in a reaction that produces or consumes gas is: H = U + ngRT

And the combustion reaction of D-ribose (C5H10O5) is: C5H10O5 (s) + 5O2 (g) 5CO2 (g) + H2O (l) ng = 5 -5 = 0, since there is no change in the number of moles of gas rH = rU = -2127 kJ.mol-1