Revision on Important Concepts

P1V1 = RT1
Check the right unit to use for P and T when R = 8.314 J/mol.K is used.
Given

V2 = 2V1
Find P2 using the following equation (revise polytropic process)

P1V1 = P2V2
Calculate W using the equation given but ensure the right unit is used so that W is in J.
Then find internal energy using first law.
0

U = Q + W
3

Ans. 1499.8 J

Note that the work from stirrer is not the same as the work of gas. Do
not assume W = 0 for part (b) U = Q + W = Q + Wgas + Wstirrer

S = C P ln

T2
P
R ln 2
T1
P1

Or, derive the following equation from dS = dQ/T and dU = dQ + dW

S = CV ln

T2
V
+ R ln 2
T1
V1

Important: Do not assume 1 mol. Check if amount or volume is informed.

In this case, calculate the no. of mole since volume is given.

PV t = nRT
U = nCV (T2 T1 )
4

Ans. 20.79 J/K for both (a) and (b)

There are many ways to prove this equation.

You may start with either of the following together with use of Maxwells equations.

U = U (T ,V )
U
U
dU =
dT +
dV
T V
V T

S = S (T ,V )
S
S
dS =
dT +
dV
T V
V T

dU = TdS PdV
5

Ans. 331.2 K, y1 = 0.67, y2 = 0.33

6

BUBL P / DEW P Calculation

Modified Raoult' s Law : yi P = xi i Pi sat

P = x1 1 P1sat + x2 2 P2sat
P=

1
y1
y2
+
sat
1 P1
2 P2sat

BUBL T Calculation
(1. by iteration to convergence)
Ti

sat

Bi
=
Ci
Ai ln P

1. Estimate initial T by T = x1T1sat + x2 T2sat , given constant P

2. Find A, 1 , 2 , and P1sat /P2sat from initial T

3. Find new P1sat from
P1sat

P
=
x1 1 + x2 2 /

4. Find new T by inserting P1sat from Step 3 into Antoine equation

5. Return to Step 2 but find those values from new T

BUBL T Calculation
(2. by trial)
Ti

sat

Bi
=
Ci
Ai ln P

1. Estimate initial T by T = x1T1sat + x2 T2sat , given constant P

2. Find A, 1 , 2 , P1sat and P2sat from initial T

3. Substitute into BUBL P equation to see if it is equal to given P
sat
1 1 1

P = x P

sat
2 2 2

+x P

4. If not, reguess a new T (depending on calculated P from Step 3)

Solution Thermodynamics

Chemical potential (by definition)

(nG )
i

ni T , P ,n
j

the change in energy when an infinitesimal number of particles of

species i is added at const T & P

At equilibrium, i = i
Partial property (by definition)
(nM )
Mi

ni T , P ,n
j

Measure of response of total property nM to the addition at const T & P

of a differential amount of species i to a finite amount of solution

Solution Thermodynamics
From nM = (T,P,n1,n2 ,...,ni ,...)

Total property from summability relation

M = xi M i
i

Gibbs/Duhem equation
M
M
i xi dM i = P dP + T dT
T ,x
P, x

Must be satisfied for all changes in P, T, and partial property in a

homogeneous phase

x dM
i

= 0 (at const T & P)

Solution Thermodynamics

Partial property for binary system at const T & P

dM
M 1 = M + x2
dx1
dM
M 2 = M x1
dx1

Solution Thermodynamics

Parallelism
nH = nU + P(nV ) vs. H i = U i + PVi

Ideal gas mixture model: Gibbs theorem

M

ig
i

(T , P ) = M (T , pi )
ig
i

provided that M

ig
i

Apply to get partial properties from pure-species properties

Calculate H iig , Siig , Giig from H iig , Siig , Giig

Combined with summability relation to get solution properties

Calculate H ig , S ig , G ig from H iig , Siig , Giig

Vi

ig

Solution Thermodynamics

Fugacity, f vs. fugacity coefficient, = f/P

an ideal gas, f = P and = f/P = 1

For a real gas, f = P (for simplicity, i is omitted)
P
GR
dP
 Knowing
ln =
= (Z 1)
0
RT
P

For

 At

any P, use cubic equations of state

ln = Z 1 ln (Z ) qI
or generalized correlation for Z

= ( )(
0

 At

low to moderate P, use generalized correlation for B

Pr 0
1
= exp B + B
Tr

Solution Thermodynamics

Fugacity, f vs. fugacity coefficient, = f/P

an ideal gas, f = P and = f/P = 1

For a real gas, f = P (for simplicity, i is omitted)

For a pure liquid,

For

ni nio + vi
yi = =
n no + v

(single reaction)

ni ni0 + j vi , j j
yi = =
n n0 + j v j j

(multireaction)
i = species
j = reaction index

P
i

i ( yii ) = P o K
16

(x )
i i

=K
Ans. 70%