Thermodynamic State of a System

The thermodynamic state of a system is defined by a few

measurable macroscopic properties.

How much?
How big?
How hot? T
P A
Etc…
S G
U V
H
THERMODYNAMIC PROPERTIES
e.g. Thermodynamic Properties of Water
T = 50 C P = 12.349 kPa
Property Saturated Liquid Saturated Vapor

Specific volume
0.001012 12.03
(m3/kg)
Internal energy
209.32 2443.5
(kJ/kg)
Enthalpy (kJ/kg) 209.33 2592.1
Entropy (kJ/kg K) 0.7038 8.0763
 ?
What happens when two pure substances are mixed?
 Mixing Water with Other Substances
WATER OTHER SUBSTANCE)
(Component 1) (Component 2)
θ1 θ2
N1 N2
θ mole fraction of i in mixture
N
x i = i additional
N state variable

Let θ - any extensive thermodynamic property

underscore - quantity per mole of substance
 Mixing Water with Methanol

(1) (2)
 Mixing Water with Methanol at 298.15K
WATER METHANOL
(Component 1) (Component 2)
V1 V2

N1 N2
V

m3 m3
V 1 = 18.0686 × 10 −6 V 2 = 40.7221 × 10 −6
mol mol
Pure Substance 1: H2O Pure Substance 2: CH3OH

Molar Volume at 298.15 K Molar Volume at 298.15 K

cm 3 cm 3
V 1 = 18.0686 V 2 = 40.7221
mol mol
Mixing Water and Methanol (T=298.15 K)

+
N1=0.85 mol N2=0.15 mol
The total volume of the mixture will be ________.
The molar volume of the mixture will be _______.
Given the molar volume and the number of moles of each
component, complete the table and then compare your results with
the values given in the next slide..
x1 (mol fraction) V= 𝑥𝑥1 V1 + 𝑥𝑥2 V2
0.00
0.12
0.22
0.28
0.37
0.41
0.53
0.61
0.72
0.85
0.94
1.00
Comparing your results with experimental data:
Molar Volumes of Water-Methanol Mixtures at 298.15 K
x1 V(cm3/mol) V – (x1V1+x2V2)
0.00 40.7221
0.12 37.7015
0.22 35.0219
0.28 33.5007
0.37 31.3572
0.41 30.2812
0.53 27.7895
0.61 25.9108
0.72 23.5759
0.85 20.9986
0.94 19.0772
1.00 18.0686
What do you observe? What are the practical implications?
PRACTICAL PROBLEM
The need arises in a laboratory
for 2,000 cm3 of an antifreeze
consisting of a 30 mole-
percent solution of methanol
in water. What volumes of
pure methanol and of pure
water at 25oC must be mixed
to form the 2,000 cm3 of
antifreeze, also at 25oC?
Experimental Data:
Molar Volumes of Water-Methanol Mixtures at 298.15 K

x1 V(cm3/mol)
0.00 40.7221 Observation:
0.12 37.7015
0.22 35.0219 V ≠ x1V 1 + x 2V 2
0.28 33.5007
0.37 31.3572 Question:
0.41
0.53
30.2812
27.7895
Why? How come?
0.61 25.9108
0.72 23.5759
0.85 20.9986
0.94 19.0772
1.00 18.0686
MOLECULAR INTERACTIONS
(1-1)
Pure property preserved.

(2-2)
Pure property preserved.

(1-2) Pure property changed

upon mixing.
V ≠ x1V 1 + x 2V 2

V − ( x1V 1 + x 2V 2 ) = ∆ mix V

VOLUME CHANGE ON MIXING

V =?
c
∆ mixV = V − ∑ x i V i
i =1
PROPERTY
CHANGES
ON MIXING
Property Changes on Mixing
Volume Change on Mixing
c
∆ mixV = V − ∑ x i V i
i =1

c
V = ∑ xi V i
i =1

partial molar volume

(note the overbar)
Let’s solve the problem...
The need arises in a laboratory for 2,000 cm3 of an antifreeze
consisting of a 30 mole-percent solution of methanol in water.
What volumes of pure methanol and of pure water at 25oC must
be mixed to form the 2,000 cm3 of antifreeze, also at 25oC.

Partial molar volumes for methanol and water in a 30 mole-

percent methanol solution at 25oC are:
Methanol(1) : 38.632 cm3/mol
Water(2): 17.765 cm3/mol

For the pure species at 25oC:

Methanol(1): 40.727 cm3/mol
Water(2): 18.068 cm3/mol
Another example from Sandler’s textbook.

Fig 8.1-2 (a) Volume change on mixing at

298.15 K: methyl formate + methanol; methyl
formate + ethanol.
We generalize the relationship for all extensive
thermodynamic properties…

c
∆ mix θ = θ − ∑ x i θ i
i =1

c
θ = ∑ xi θ i
i =1
Mixing Water and Sulfuric Acid

+
 Mixing of Water with Sulfuric Acid
WATER H2SO4
(Component 1) (Component 2)
H1 H2

N1 N2

H
kJ kJ
H1 = 0 H2 = 0
kg kg
Empirical data

H (T , xi ) @ constant P

Fig 8.1-1 Enthalpy-concentration

diagram for aqueous sulfuric acid
at 0.1 MPa.
Enthalpy Change on Mixing
Enthalpy Change
c
∆ mix H = H − ∑ xi H i
i =1

c
H = ∑ xi H i
i =1

partial molar enthalpy

Enthalpy Change on Mixing
∆ mix H ( x1 ) = H − ( x1 H 1 + x2 H 2 )

Fig 8.6-3 Heat of mixing data for

the water(1)-methanol(2) system
at T = 19.69oC
PRACTICAL PROBLEM
[Problem 8.17, Sandler]
GIVEN:
20 wt % H2SO4 solution (5oC) + pure H2SO4 (50oC)
 60 wt % H2SO4 solution (70oC)

REQUIRED:
a. Amount pure H2SO4 to be added
b. Q (added or removed)

pure 1 + pure 2 = mixture 1

pure + mixture 1 = mixture 2
mixture 1 + mixture 2 = mixture 3
Mixing Processes
• Adiabatic
• Isothermal/Non-adiabatic
Analysis: Enthalpy Balance & Component Balance
Requirement: H(T, x) or ∆mixH(T,x) Data
 Isothermal Mixing of 2 Components/Mixtures

(Component/Mixture 1) (Component /Mixture 2)

H1 H2
N1 N2
T T
T H
Q=? xi
added/removed
Isothermal Mixing of 2 Components/Mixtures
Mixture I Mixture II
I I I II II II
H (T, xi ); N H (T, xi ); N

Q added or removed (?)

Mixture III
III III III
H (T, xi ); N
Data to be mined.

Steady-state enthalpy balance: To be determined.

I I I II II II III III III

N H (T, xi ) + N H (T, xi ) - N H (T, xi ) + Q = 0
 Adiabatic Mixing of 2 Components/Mixtures

(Component /Mixture 1) (Component /Mixture 2)

H1 H2
N1 N2
T1 T2
H xi
T =?
 Adiabatic Mixing of 2 Components/Mixtures
Mixture I Mixture II
I I I I II II II II
H (T , xi ); N H (T , xi ); N

Mixture III
III III III III
H (T , xi ); N
Data to be mined.

Steady-state enthalpy balance: To be determined.

I I I I II II II II III III III III

N H (T , xi ) + N H (T , xi ) - N H (T , xi ) = 0
Interpreting H(T,x) diagram
∆ H = (x H + x H ) − (x H + x H )
mix 1 1 2 2 1 1 2 2

For an ideal solution, isotherms on an

enthalpy-concentration diagram are c
straight lines connecting the enthalpy (x1 H 1 + x 2 H 2 )
c
of pure species 2 at x1 = 0 with the c
enthalpy of pure species 1 at x1 = 1. ∆ mix H

The point on an H-x diagram which (x H

1 1 + x2 H 2 )
represents a solution formed by
adiabatic mixing of two other solutions
must lie on the straight line connecting
the points representing the two initial
solutions.
[Problem 8.17, Sandler]

20 wt % H2SO4 solution (5oC)

+
pure H2SO4 (50oC)

60 wt % H2SO4 solution (70oC)

a. Amount pure H2SO4 to be added

b. Q (added or removed)
What if only ∆mixH data (not H data) are available?

Exercise: Problem 8.29, Sandler.

Property Changes on Mixing
c
∆ mix θ = θ − ∑ x i θ i
i =1

c
θ = ∑ xi θ i
i =1

Partial Molar Property

We take this up next in more detail.