Scribd
Upload
167 views4 pages

Test 3 Solution 2010 PDF

(1) The document provides the solution to a chemistry exam with 3 questions on thermodynamics. (2) Question 1 defines equations for changes in thermodynamic properties in terms of temperature and pressure. Question 2 shows how to derive expressions for pressure, entropy, internal energy, enthalpy, and compressibility factor in terms of the Helmholtz free energy. (3) Question 3 estimates properties for the compression of propane gas using provided data and correlations. It finds the molar volume is 209 cm3/mol, the enthalpy change is 8944 J/mol, and the entropy change is -10.83 J/(mol K).

Uploaded by

Manishaa Varatha Raju
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
167 views4 pages

Test 3 Solution 2010 PDF

(1) The document provides the solution to a chemistry exam with 3 questions on thermodynamics. (2) Question 1 defines equations for changes in thermodynamic properties in terms of temperature and pressure. Question 2 shows how to derive expressions for pressure, entropy, internal energy, enthalpy, and compressibility factor in terms of the Helmholtz free energy. (3) Question 3 estimates properties for the compression of propane gas using provided data and correlations. It finds the molar volume is 209 cm3/mol, the enthalpy change is 8944 J/mol, and the entropy change is -10.83 J/(mol K).

Uploaded by

Manishaa Varatha Raju
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 4

CHE 3161: Chemistry & Chemical Thermodynamics

Test 3 - Solution

Date: 14/04/2010 Total Marks: 30


The exam is open book and notes.

1) In general for an arbitrary thermodynamic property of a pure substance, M = M(T, P );


whence,    
∂M ∂M
dM = dT + dP
∂T P ∂P T
For what two distinct conditions is the following equation true?
Z T2  
∂M
∆M = dT
T1 ∂T P

(4 marks)

Solution: The given equation will be true if and only if


 
∂M
dP = 0
∂P T

The two circumstances for which this condition holds are when
 
∂M
(i) =0
∂P T

or when,
(ii) dP = 0
The former is a property feature, and the latter is a process feature.
2) A pure substance is described by an expression for A(T, V ). Show how to determine P , S,
U, H and Z, in relation to A, T and V , and/or derivatives of A with respect to T and V .
(6 marks)

Solution: From the definition of the Helmholtz free energy,

A=U −T S

we have,
dA = −P dV − S dT (1)
Further, since A = A(T, V ), it follows that,
   
∂A ∂A
dA = dV + dT (2)
∂V T ∂T V

Comparing equations (1) and (2), leads to,


   
∂A ∂A
P =− and S=−
∂V T ∂T V

Since U = A + T S, it follows that,


 
∂A
U =A−T
∂T V

By the definition of the enthalpy, H = U + P V , it follows that,


   
∂A ∂A
H =A−T −V
∂T V ∂V T

Finally, since Z = P V /RT ,


 
V ∂A
Z =−
RT ∂V T
3) Propane gas at 1 bar and 35◦ C is compressed to a final state of 127.5 bar and 208◦C.
Estimate the molar volume of propane in the final state and the enthalpy and entropy changes
for the process, using the Lee/Kesler generalized-correlation tables. In its initial state, propane
may be assumed to be an ideal gas. The ideal heat capacity for propane gas is known to depend
on temperature through the relation,
CP
= A + B T + C T2
R
where, T is in degrees Kelvin. The coefficients A, B and C, and the critical parameters for
propane are given in the Table below:

A B C
1.213 28.785 × 10−3 −8.824 × 10−6
Tc (K) Pc (bar) ω
369.8 42.48 0.152
(20 marks)

Solution: The process undergone by propane can be visualised in the following figure:

Figure 1: The enthalpy and entropy changes from the initial to the final state can be calculated by a
two-step process. The first is a change from an ideal gas at 1 bar and 35◦ C to an ideal gas at 127.5 bar
and 208◦ C. The second is a change from an ideal gas at 127.5 bar and 208◦ C to a real gas at 127.5 bar
and 208◦ C.

For the given data,


T2 481.15
T2r = = = 1.3
Tc 369.8
P2 127.5
P2r = = = 3.0
Pc 42.48
From the Lee/Kesler generalized-correlation tables in Appendix E of SVA, at these values of Tr
and Pr ,
Z 0 = 0.6344 ; and Z 1 = 0.2079
Since,
Z = Z0 + ω Z1
we have, Z = 0.6344 + 0.152 × 0.2079 = 0.666.

Further,
Z RT 0.666 × 83.14 × 481.15
V = = = 209 cm3 /mol
P 127.5

Also, from the Lee/Kesler generalized-correlation tables,


0 1
H2R H2R
= −2.274, and = −0.3
R Tc R Tc
0 1
S2R S2R
= −1.299, and = −0.481
R R
As a result, since,
0 1 0 1
H2R = H2R + ω H2R and S2R = S2R + ω S2R

we have,
H2R = −2.274 × 8.314 × 369.8 + 0.152 × (−0.3 × 8.314 × 369.8)
= −6991.452 − 0.152 × 922.355 = −7131.65 J/mol

S2R = −1.299 × 8.314 + 0.152 × (−0.481 × 8.314)


= −10.8 − 0.152 × 4.0 = −11.41 J/(mol K)

For an ideal gas, with the coefficient D = 0,

∆H ig B C
= A (T2 − T1 ) + (T22 − T12 ) + (T23 − T13 )
R 2 3
∆S ig
   
T2 C 2 2 P2
= A ln + B (T2 − T1 ) + (T2 − T1 ) − ln
R T1 2 P1
It follows that,

∆H ig 28.785 × 10−3 
(481.15)2 − (308.15)2

= 1.213 (481.15 − 308.15) +
R 2
−8.824 × 10−6 
(481.15)3 − (308.15)3 = 1933.56

+
3
ig
which implies, ∆H = 16075.65 J/mol.

Therefore,
∆H = ∆H ig + H2R = 16075.645 − 7131.65 = 8944 J/mol

In a similar manner, ∆S ig = 0.0697 × 8.314 = 0.5798 J/(mol K), and,

∆S = ∆S ig + S2R = 0.5798 − 11.41 = −10.83 J/(mol K)

You might also like