28 February 2014, MAFabro

Todays topics
Finding the activity coefficient
Partial molar quantities
Gibbs-Duhem equation

Problem: Activity
A stream of argon gas is passed in a
closed system over a boat containing
mercury at 273 K. The flow rate of argon
is slow enough to allow this gas to
become saturated with mercury vapor.
The volume of argon used was measured
at 293.15K, and was found to be 22 L. The
argon was found to contain 0.0674 grams
of mercury. Solve for the saturated
pressure of pure mercury.

Problem: Activity
The same experiment is carried out
with a sodium amalgam (Na + Hg) in
which the atomic fraction of sodium is
0.122. Twenty-two liters of argon gas
was found to be saturated with 0.0471
grams of mercury. Find the activity
coefficient of Hg at this concentration.

Question 1. Pure water

One mole of pure water is 18
mL. If 1 mole of water is added
to 10 liters of water, what is the
total volume?

Question 1. Pure water

One mole of pure water is 18
mL. If 1 mole of water is added
to 10 liters of water, what is the
total volume?
ANSWER: 10.018 L

Question 2. Pure ethanol

One mole of pure ethanol is 58
mL. If 1 mole of ethanol is added
to 10 liters of ethanol, what is the
total volume?

Question 2. Pure ethanol

One mole of pure ethanol is 58
mL. If 1 mole of ethanol is added
to 10 liters of ethanol, what is the
total volume?
ANSWER: 10.058 L

Game?

Question 3.
One mole of pure water is 18
mL. If 1 mole of water is added
to 10 liters of ETHANOL, what is
the total volume?

Question 4.
One mole of pure ethanol is 58
mL. If 1 mole of ethanol is added
to 10 liters of WATER, what is the
total volume?

Question 5.
One mole of pure water is 18 mL. If
1 mole of water is added to 10 liters
of a 40% ethanol-60% water solution,
what is the total volume?

Question 6.
One mole of pure water is 18 mL. If
1 mole of water is added to 10 liters
of a 80% ethanol-20% water solution,
what is the total volume?

Question 7.
One mole of pure ethanol is 58 mL.
If 1 mole of ethanol is added to 10
liters of a 40% ethanol-60% water
solution, what is the total volume?

Question 8.
One mole of pure ethanol is 58 mL.
If 1 mole of ethanol is added to 10
liters of a 80% ethanol-20% water
solution, what is the total volume?

Answers!

Question 3.
One mole of pure water is 18
mL. If 1 mole of water is added
to 10 liters of ETHANOL, what is
the total volume?
ANSWER: 10.014 L

Question 4.
One mole of pure ethanol is 58
mL. If 1 mole of ethanol is added
to 10 liters of WATER, what is the
total volume?
ANSWER: 10.054 L

Question 5.
One mole of pure water is 18 mL. If
1 mole of water is added to 10 liters
of a 40% ethanol-60% water solution,
what is the total volume?

ANSWER: 10.0172 L

Question 6.
One mole of pure water is 18 mL. If
1 mole of water is added to 10 liters
of a 80% ethanol-20% water solution,
what is the total volume?

ANSWER: 10.0155 L

Question 7.
One mole of pure ethanol is 58 mL.
If 1 mole of ethanol is added to 10
liters of a 40% ethanol-60% water
solution, what is the total volume?

ANSWER: 10.0565 L

Question 8.
One mole of pure ethanol is 58 mL.
If 1 mole of ethanol is added to 10
liters of a 80% ethanol-20% water
solution, what is the total volume?

ANSWER: 10.0578 L

Partial Molar Volume

Volume contribution of a mole of a
substance added to a very large
volume of a specific solution

Total or integral quantity

vs. Partial molar quantity

For any extensive

thermodynamic quantity Y,
at constant p and T, for a
system with components A
and B:

Relationship between total

and partial quantities:

Problem 1
The integral enthalpy of mixing of liquid (Cu, Zn)
solution can be approximated by the following
equation Cu(l) and Zn(l) as reference states:
mixHm = -19250xCuxZn J/mol at 1400 K
a. Derive the corresponding partial quantities of
Cu and Zn
b. Show that the two partial equations are
internally consistent with the Gibbs-Duhem
equation

Enthalpy of mixing (Total

quantity)

with the partial molar

enthalpy of mixing of Cu

and partial molar

enthalpy of mixing of Zn

Seatwork (Warnes)
Using the free energy diagram for the
Cu-Ni system below, sketch on the accompanying
graph the partial molar free energy of Ni as a
function of composition.
What is the partial
molar free energy of
Cu and Ni in a
sample that is 30 at.
% Cu?
What is the free
energy of 1 mole of
the same alloy?

Gibbs-Duhem Equation
Helps us calculate relationships between
quantities as a system remains in equilibrium
Helpful in calculating the partial molar quantity
of a binary mixture by measuring the
composition of the mixture
Helpful in calculating partial vapor pressures by
calculating the total vapor pressure

0 = n i dYi
i

For a two component

system:

n A dYA + n B dYB = 0

Problem
The experimental value of the partial molar
volume (mL) of K2SO4(aq) at 298 K is given by
the expression

VA = 32.280 +18.216b1/ 2

Where b is the numerical value of molality of

K2SO4. Use the Gibbs-Duhem equation to derive
an equation for the partial molar volume of water
in the solution. The molar volume of pure water
at 298 K is 18.079 mL.

Central Michigan University