SIMPLE

MIXTURES
THERMODYNAMIC DESCRIPTION OF
MIXTURES
DR.NOORASHIKIN MD SALEH

ARYO ABYOGA A (080358395)

GERALD MAYO L (0806472212)
LEONARD AGUSTINUS J (0806472225)
Simple Mixtures
¨ Often in chemistry, we encounter mixtures of
substances that can react together.
¨ We shall mainly consider binary mixtures – mixtures
of two components.

xA + xB = 1
 Dalton’s Law
¨ The total pressure is the sum of all the partial
pressure.
¨ We already used mole fraction to descrice the
partial pressure of mixtures of gases which refers
to a total pressure

pj = x j p
pA + pB + L = (x A + x B + L ) p = p
 partial molar volume

The partial molar volume is the contribution that one component in a

mixture makes to the total volume of a sample
H2O EtOH
Add 1.0 mol H2O Add 1.0 mol H2O
Volume increases
by 18 cm3 mol-1
Volume increases
by 14 cm3 mol-1
Molar volume of H2O:
18 cm3 mol-1
Partial molar volume of
H2O in EtOH: 14 cm3 mol-1

The different increase in total volume in the H2O/EtOH example depends

on the identity of the molecules that surround the H2O. The EtOH
molecules pack around the water molecules, increasing the volume by
only 14 cm3 mol-1
Partial molar volume of substance A in a mixture is the change in volume
per mole of A added to the large volume of the mixture
Partial Molar Volumes
¨ Imagine a huge volume of pure water at 25 °C. If
we add 1 mol H2O, the volume increases 18 cm3 (or
18 mL).
¨ So, 18 cm3 mol-1 is the molar volume of pure water.
Partial Molar Volumes
¨ Now imagine a huge volume of pure ethanol and
add 1 mol of pure H2O it. How much does the total
volume increase by?
Partial Molar Volumes
¨ When 1 mol H2O is added to a large volume of
pure ethanol, the total volume only increases by ~
14 cm3.
¨ The packing of water in pure water ethanol (i.e. the
result of H-bonding interactions), results in only an
increase of 14 cm3.
Partial Molar Volumes
¨ The quantity 14 cm3 mol-1 is the partial molar
volume of water in pure ethanol.
¨ The partial molar volumes of the components of a
mixture varies with composition as the molecular
interactions varies as the composition changes from
pure A to pure B.
 æ ¶V ö
VJ = ç ÷
è ¶n J ø p,T ,n'

The partial molar volume of

components of a mixture vary as the
mixture goes from pure A to pure B -
that is because the molecular
environments of each molecule change
(i.e., packing, solvation, etc.)
Partial molar volumes of a water-
ethanol
binary mixture are shown
at 25 oC across all possible
Compositions. The Partial molar
volume, Vj, of a substance j define as :
The partial molar volume is the slope of
a plot of total volume as the
amount of J in the sample is changed
(volume vs. composition)

Partial molar volumes vary with

composition (different slopes at
compositions a and b) - partial molar
volume at b is negative (i.e., the
overall sample volume decreases as
A is added)
Partial Molar Volumes
n When a mixture is changed by dnA of A and dnB
of B, then the total volume changes by:
æ ¶V ö æ ¶V ö
dV = ç ÷ dn A + ç ÷ dn B
è ¶n A ø p,T ,n B è ¶n B ø p,T ,n A
If partial molar volumes are known for the two
components, then at some temperature T, the
total volume V (state function, always positive)
of the mixture is
Partial Molar Volumes

æ ¶V ö æ ¶V ö
dV = ç ÷ dn A + ç ÷ dn B
è ¶n A ø p,T ,n B è ¶n B ø p,T ,n A
dV = VA dn A + VB dn B

ò ò
nA nB
V= VA dn A + VB dn B
0 0
Partial Molar Volumes

ò ò
nA nB
V= 0
VA dn A + 0
VB dn B

ò ò
nA nB
V = VA 0
dn A + VB 0
dn B
V = VA n A + VB n B
Exercise
¨ • P9.18) The partial molar volumes of ethanol in a
solution with = 0.60 at 25ºC are 17 and 57 cm3
mol–1, respectively. Calculate the volume change
upon mixing sufficient ethanol with 2 mol of water
to give this concentration. The densities of water
and ethanol are 0.997 and 0.7893 g cm–3,
respectively, at this temperature.
Solution
Exercise
Solution
 Partial Molar Volumes
V (NaCl, aq) = volume of sodium chloride solution
_
V (NaCl, aq) = partial molar volume of sodium chloride
in water
Partial Molar Volumes
¨ How to measure partial molar volumes?
¨ Measure dependence of the volume on composition.
¨ Fit a function to data and determine the slope by
differentiation.
 Partial Molar Volumes
¨ Ethanol is added to 1.000 kg of water.
¨ The total volume, as measured by experiment, fits
the following equation:

V = 1002.93 + 54.6664 x - 0.36394 x + 0.028256 x

2 3

x = nE
Partial Molar Volumes
æ ¶V ö æ ¶V ö
VE = ç ÷ =ç ÷
è ¶n E ø p,T ,n w è ¶x ø p,T ,n w
dV
= 54.6664 - (2)0.36394 x + (3)0.028256x 2

dx
Partial Molar Volumes
¨ Molar volumes are always positive, but partial
molar quantities need not be. The limiting partial
molar volume of MgSO4 in water is -1.4 cm3mol-1,
which means that the addition of 1 mol of MgSO4 to
a large volume of water results in a decrease in
volume of 1.4 cm3.
exercise
¨ A binary mixture contains 4 moles of substance A
and 6 moles of substance B. Express the composition
of the mixture using mole fraction and mole percent.
solution
¨ xi = ni/n ,
¨ the amount of substance in the mixture is n = 4+6 =
10 mol.
¨ Thus, we get xA = 4/10 = 0.4, xB = 6/10 = 0.6.
¨ The mixture contains 40 mole percent of substance
A, and 60 mole percent of substance B.
exercise
¨ A mixture contains 5 g of substance A with a molar
mass MA = 25 g mol−1 , and 15 g of substance B
with a molar mass MB = 75 g mol−1 . Calculate the
mass fractions and the mole fractions.
Solution
¨ Substituting into (1.8) wi = mi/m ,
¨ gives wA = 5/(5 + 15) = 0.25 , wB = 15/(5 + 15)
= 0.75 .
¨ We calculate the mole fractions
¨ xA =(0.25/25)// ((0.25/25) + (0.75/75)) = 0.5 ,
¨ xB = (0.75/75)//((0.25/25) + (0.75/75)) = 0.5
Partial Molar Gibbs energies
¨ The concept of partial molar quantities can be
extended to any extensive state function.
¨ For a substance in a mixture, the chemical potential
is defined as the partial molar Gibbs energy.

æ ¶G ö
µJ = ç ÷
è ¶n J ø p,T ,n'
Partial Molar Gibbs energies
¨ For a pure substance:

G = n J GJ ,m

æ ¶G ö æ ¶n J GJ ,m ö
µJ = ç ÷ =ç ÷ = GJ ,m
è ¶n J ø p,T ,n' è ¶n J ø p,T ,n'
Partial Molar Gibbs energies
¨ Using the same arguments for the derivation of
partial molar volumes,
G = nAµA + nBµB

¨ Assumption: Constant pressure and temperature

 Partial Molar Gibbs energies
Fundamental equation of chemical thermodynamics
dG = Vdp - SdT + µA dn A + µB dn B + "

dG = µA dn A + µB dn B + " (at constant p and T)

!!dw add,max = µA dn A + µB dn B + " (at constant p and T)
 Chemical Potential
G = H - TS = U + pV - TS
U = - pV + TS + G
dU = - pdV - Vdp + SdT + TdS + dG
dU = - pdV - Vdp + SdT + TdS + (Vdp - SdT + µA dn A + µB dn B + ")
dU = - pdV + TdS + (µA dn A + µB dn B + ")

dU = µA dn A + µB dn B + " (at constant S and V)

æ ¶U ö
µJ = ç ÷
è ¶n J ø S,V ,n'
!!
Chemical Potential

æ ¶H ö æ ¶A ö
µJ = ç ÷ µJ = ç ÷
è ¶n J ø S, p,n' è ¶n J øV ,T ,n'
Gibbs-Duhem equation
G = n A µA + n B µB
dG = n A dµA + n B dµB + µA dn A + µB dn B

dG = µA dn A + µB dn B (at constant p and T)

n A dµ A + n B dµ B = 0
å n dµ
J J =0
J
Gibbs-Duhem equation

n A dµ A + n B dµ B = 0
nA
dµ B = - dµ A
nB
Molarity and Molality
¨ Molarity, c, is the amount of solute divided by the
volume of solution. Units of mol dm-3 or mol L-1.
¨ Molality, b, is the amount of solute divided by the
mass of solvent. Units of mol kg-1.
Exercise
¨ A total of 58.5 g of NaCl has been mixed with 500
g of water. Calculate the molality of sodium
chloride given that you know its molar mass to be M
= 58.5 g mol−1
Solution
¨ By substituting into formula, mi = ni/msolvent

¨ we obtain mNaCl = (58.5/58.5)// 0.500 = 2 mol

kg−1 .
¨ The molality of the obtained solution is 2 mol kg−1 .
Thermodynamics of mixing
¨ So we’ve seen how Gibbs energy of a mixture
depends on composition.
¨ We know at constant temperature and pressure
systems tend towards lower Gibbs energy.
¨ When we combine two ideal gases they mix
spontaneously, so it must correspond to a decrease
in G.
Thermodynamics of mixing
Thermodynamics of mixing

q p
Gm = Gm + RT ln q
p
q p
µ = µ + RT ln q
p
µ = µq + RT ln p
Thermodynamics of mixing
µ = µq + RT ln p
Gi = n A (µqA + RT ln p)+ n B (µqB + RT ln p)
G f = n A (µ + RT ln pA )+ n B (µ + RT ln pB )
q
A
q
B

pA pB
D mixG = n A RT ln + n B RT ln
p p
Thermodynamics of mixing
pA pB
D mixG = n A RT ln + n B RT ln
p p
pA pA
= xA = xB
p p
D mixG = n A RT ln x A + n B RT ln x B
xA n = nA x B n = nB
D mixG = nRT (x A ln x A + x B ln x B )
D mixG < 0
Thermodynamics of mixing
Gibbs energy of mixing
¨ A container is divided into
two equal compartments.
One contains 3.0 mol
H2(g) at 25 °C; the other
contains 1.0 mol N2(g) at
25 °C. Calculate the
Gibbs energy of mixing
when the partition is
removed.
 Gibbs energy of mixing
Gi = 3.0(µqH 2 + RT ln 3p)+ 1.0(µqN 2 + RT ln p)
G f = 3.0(µqH 2 + RT ln 3 2 p)+ 1.0(µqN 2 + RT ln1 2 p)
3 1
p 2 p
D mixG = 3.0(RT ln 2
) + 1.0(RT ln )
3p p
D mixG = 3.0(RT ln 12 ) + 1.0(RT ln 12 )
D mixG = -6.9 kJ

¨ Two processes:
1) Mixing
2) Changing pressures of the gases.
Gibbs energy of mixing

D mixG = nRT (x A ln x A + x B ln x B ) p
3 1
D mixG = 3.0(RT ln ) + 1.0(RT ln )
4 4
D mixG = -2.14 kJ - 3.43 kJ
D mixG = -5.6 kJ

p
 Multiple Choice Exercises
1) When 15.0 cm3 of benzene, C6H6, is added to 125 cm3
of water, H2O, at 20°C, the final volume of the liquid
mixture is 137 cm3. Calculate the partial molar volume
of benzene in dilute aqueous solutions given that the
density of benzene and of water are 0.879 g cm–3 and
0.998 g cm–3 respectively, and the partial molar
volume of water is 17.8 cm3 mol–1 at this temperature.
a. 88.9 cm3 mol–1
b. 81.8 cm3 mol–1
c. 14.6 cm3 mol–1
d. 86.8 cm3 mol–1
2) Calculate the change in the chemical
potential of a perfect gas when its partial
pressure doubles at a temperature of
200°C.
a. +2.73 kJ mol–1
b. +1.15 kJ mol–1
c. +0.50 kJ mol–1
d. +0.30 kJ mol–1
Answer Q1
Answer Q2
 Assignment 1
Question 1
The partial molar volumes of propanone and
trichloromethane in a mixture in which the mole
fraction of CHCl3 is 0.4693 are 74.166 and
80.235 cm3 mol-1,respectively. What is the
volume of a solution of total mass 1.000 kg?
 Assignment 1
• Question 2
• Calculate (a) the (molar) Gibbs energy of
mixing, when the two major components of air
(nitrogen and oxygen) are mixed
• to form air at 298 K. The mole fractions of N2
and O2 are 0.78 and 0.22,
• respectively. Is the mixing spontaneous?