Chem 467

Fall 2012

Problem Set #11 key

1. Problem 1.2 f) Discuss the sign of each of the results in the previous calculations. First, we need to determine the number of moles of ethyl alcohol. The molar mass is 46.1 g mol -1, n =1000 g 1 mol = 21.7 mol 46.1 g

a) Since this process is at constant pressure, q = H. Given vapH, for the condensation process q =n vap H o =21.7 mol 42.3 kJ mol1 q = 918 kJ b) Since the process occurs at constant external pressure w = pex V The work involved in this process is due to the change in volume from gas to liquid. The volume of the gas is simply n R T 21.7 mol 0.08206 L atm mol1 K 1 351.65 K V g= = =626.2 L p 1 atm We have the density of the liquid, so the liquid volume is 1L V l =1.00 kg =1.28 L 0.78 kg The work is then w = 1 atm 1.28 L626.2 L =624.9 L atm w = 63.3 kJ c) The change in internal energy is simply U = q + w = 855 kJ d) Since this is a reversible phase change, the entropy is simply given by H 918 kJ = = 2610 J K-1 T 351.65 K e) Since the process is reversible, G = 0. S= f) q < 0, because we are going form vapor to liquid. Condensation required heat be removed from the system. w > 0, because we are going from large volume to small volume. Work is done on the system. U < 0, again because we are going from vapor to liquid. Interactions are stronger in the liquid than in the vapor, which lowers the energy. S < 0, again because we are going from vapor to liquid. There are fewer possible states for a liquid than for a vapor, or the disorder decreases. G = 0, because the process was reversible and at the standard phase transition temperature. 8.3145 J 0.08206 L atm

2. Problem 1.14 a) The constant pressure heat capacity is defined as The enthalpy, or the heat, is given by H =T C p dT =T a 2 b T c T 2 dT
1 1

C p=

H T

T2

T2

2 H = a T 2 T 2 b [T 2 2T 1 ] c

1 1 T 2 T1

]
Cp,m = 24 kJ mol-1 K-1

b) Using the values given for Mg (s), we readily have 3. Problem 1.16 We are told to consider S(T, p), so we write the total differential as dS =

S T dT
p

S dp p T dS =

q rev T If a process is at constant pressure, the heat is the enthalpy, so we can write C S dH C p = p dS = = dT or T p T T T That takes care of the first term. Now, for the second, it looks like we need a Maxwell relation. Starting with the Gibbs equation for the Gibbs energy, we have S V = =V dG =S dT V dp which gives us p T T p where we use the definition of the thermal expansion coefficient Let's look at the definition of S

Substitution of these two results gives us Multiplying through by T gives the desired relation Q.E.D. 4. Problem 1.18 a) The change of state is b) Start with

dS =

Cp dT V dp T T dS =C p dT T V dp

2 ideal gas (g) [330 K, 3.50 atm] 2 ideal gas (g) [330 K, p2]

dU = T dS p dV

Since the gas is ideal, the internal energy only depends on T, and since this process is isothermal, dU = 0. This gives us
T dS = p dV

or

dS =

p R dV = dV T V

V R dV = R ln 2 V V1 We have pressure data rather than volume data, but they are directly proportional, so we can write The total change is the integral of this expression S =V
V2
1

p S = R ln 1 p2

p1 S 12.5 J mol1 J 1 ln = = =1.503 p2 R 8.3145 J mol 1 K 1 p1 = 4.497 p2 p2 = 0.778 atm

c) For the Gibbs energy, we start with Since T is constant, we have

dG =S dT V dp

dG =V dp=

n RT dp p p2 p1

Integrating gives us Substituting in gives

G= n R T ln G = 8250 J

5. Problem 1.20 g) Calculate Stot for the same process and comment on the spontaneity of this process. Clearly state any assumptions. a) Since the pressure is constant, we can use Charles' law to determine the final temperature. Since the volume has increased by a factor of 4, the temperature must also increase by a factor of 4, so Tf = 1193 K The change is given by NH3 (g) [1 bar, 298.15 K] NH3 (g) [1 bar, 1193 K] b) We use the constant pressure heat capacity and integrate over the temperature change q =T
T2
1

33103 2 2 C p , m dT = 25.9 [ T 2T 1 ] [T 1 T 2 ] 2

q = 45.19 kJ mol-1 c) Since we are doing this process at constant pressure, From the ideal gas law, we can write So the work can be written as d) The enthalpy change is simply the heat RT V m= p w = pex V or V m= R T p

w = R T = 7439 J mol-1 H = 45.19 kJ mol-1

e) The internal energy change is simply f) To calculate the entropy, we evaluate S =T

T2
1

U = q + w = 37.76 kJ mol-1

Cp ,m T dT =25.9 ln 2 33103 T 2T 1 T T1

S = 65.44 J mol-1 K-1 g) In order to calculate the entropy of the surroundings, we need to assume a path for the process. The simplest possible path would be to assume that the surroundings are at constant 1193 K. The entropy is then given by q sys 45.19 kJ mol 1 1 1 S sur = = =37.88 J mol K T 1193 K The total entropy is then Stot = 65.44 37.88 = 27.56 J mol-1 K-1. Because the total entropy is positive, the gas spontaneously expands when heated. If the gas were heated in stages, the total entropy change would be less, until reversible heating would result in no entropy change of the universe. 6. Consider the following process. Take 1 mol of monatomic ideal gas at 1 L and 300 K and heat it to 600 K while expanding the volume to 2 L. Calculate the entropy for the system, surroundings, and the universe. (Assume the simplest non-reversible path for this process.) Since entropy is a state function, we can use a reversible path that connects the initial and final states. V S 1= R ln 2 For a reversible, isothermal expansion we have V1 For the heating, So the total entropy is given by If we put in our numbers, we get T2 T2 S 2=3 / 2 R ln = R ln T1 T1 V2 T2 S sys= R ln R ln V1 T1 Ssys = 14.4 J K-1.

3/ 2

V 2 T2 = R ln V 1 T1

3/ 2

3/ 2

Now, for the surroundings we need to know the actual amount of heat involved. Let's look at the initial and final states. We can see that both the temperature and volume have been doubled, which tells us that the initial and final pressures are the same. The simplest path will be to treat this as a constant pressure expansion of ideal gas. For constant pressure, q = H = 5/2 n R T = 6236 J. Let's treat the surroundings as being at the final temperature, so S sur = q , or 600 K

Ssur = 10.39 J K-1. The entropy of the universe is the sum of the two, or Suniv = 4.01 J K-1.

The fact that Suniv > 0 tells us that this process will occur spontaneously. 7. This problem will further explore the idea of an exact differential. a) Let's consider the molar volume to be a function of pressure and temperature. Write the total differential for molar volume. Vm V m d V m= dT dp T p p T

b) Evaluate this expression for an ideal gas. We simply take the requested derivatives from the ideal gas law, V m= RT / p

These let us write

V m R = T p p R RT dT 2 dp p p

Vm RT = 2 p T p

d V m=

c) Show that the total differential for the molar volume is an exact differential. This means that we need to show that d R d RT = 2 dp p dT p d R R = 2 dp p p d R d RT R = = 2 dp p dT p2 p Therefore, dVm is an exact differential.

d RT R = 2 dT p2 p Q.E.D.

d) Show that for a reversible process involving an ideal gas we can write RT q rev= d V mC V , m dT Vm For a reversible process we would write our equation for the First Law as d U m= qrev w rev For an ideal gas, for any process, we can write We can also write for the work d U m=C V , m dT w rev= p d V m = RT dVm Vm

Putting these into the above expression and solving for the heat gives us

 q rev=

RT d V mC V , m dT Vm

Q.E.D.

e) Show that this differential is inexact. To test for exactness, we need to determine if this equality holds true: RT = C T V m V V ,m

RT = R T V m Vm Thus, RT C T V m V V ,m

C = 0 V V ,m

and the heat is an inexact differential. f) Consider the entropy, defined as dS = differential. We write the total differential of the entropy as q rev R CV ,m dS = = d V m dT T Vm T To test for exactness, we need to show that R = C V ,m T V m V T R =0 T V m
q rev and show that this function is an exact T

C V ,m =0 V T

R = C V , m =0 T V m V T Therefore, dS is an exact differential. Q.E.D. 8. Data for the molar heat capacity of crystalline -D-glucose as a function of temperature are available in the associated txt file. In this problem we will obtain the Third Law entropy from these heat capacity measurements. We will also look at the low- T behavior of the heat capacity. (This problem is probably best done in Excel.) a) Test the behavior of this material with respect to the Debye- T 3 law. To do so, plot the data below 16 K as Cp/T vs. T 2. If the material follows this law, your data should fit to a straight line. Use a linear regression technique to obtain the slope of the curve. The intercept should be nearly zero.

Plotting the data and fitting to a line gives a slope of a = 1.3 x 10-3 J mol-1 K-4 b) Use a linear regression of the high temperature data from 288 to 307.6 K to obtain a value for Cp at 298.15 K. (This time, do a fit of Cp vs T to the high temperature data. Your objective is to be able to estimate the value of Cp at T = 298.15 K, a temperature that is not included in the data table.) The equation for the line is given on the chart. With this equation, we predict a value for C p at 298.15 K of 219.09 J mol-1 K-1

c) Add the data point you determined for 298.15 K to the data set and calculate values of Cp/T. Make a plot of Cp/T vs T.

d) Use the trapezoidal rule or some other numerical technique to integrate the graph of part c) and obtain the area under the curve from 15.29 to 298.15 K. This area corresponds to the entropy change S = (S298.15 S15.29). We can use the trapezoidal rule, which is area = 0.5*( y1+y2)*(x2-x1), to get S = 207.81 J mol-1 K-1 for the increment 15.29 to 298.15 K. e) Use the a coefficient from part a) to calculate the entropy increment ( S15.29 S0).
15.29 K Cp a 2 3 dT =0 a T dT = 15.29 K . T 3 We use our earlier value of a = 1.3 x 10-3 J mol-1 K-4 to obtain S = 1.55 J mol-1 K-1 for the interval 0 to 15.29 K.

Within the Debye approximation, we have

S =0

15.29 K

f) Combine the two increments in parts d) and e) to obtain the entropy at 298.15 K. (Assume there is no residual entropy at T = 0.) Adding the two parts together gives us S298.15 = 209.36 J mol-1 K-1. Writing Prompt Briefly describe the First and Second Laws of Thermodynamics in non-mathematical terms. As part of the discussion, provide a practical example. The First Law of Thermodynamics states that the total energy of the universe does not change. Energy can change forms, but the total amount cannot increase or decrease. The Second Law of Thermodynamics relates to the quality of that energy and how much can be utilized to perform work. Not all the available energy can be converted into work, meaning no heat engine can ever be 100% efficient.