Physical Chemistry for Engineers 2 Lecture

Rey Martin G. Estoque

Adamson University
Chemical Engineering Department
 An electrolyte is a substance that dissociates into
charged particles (ions) upon dissolution in a
compatible solvent.
 The movement of these ions give electrolytes the
ability to conduct electricity.
 Can be classified as strong or weak electrolytes.
 Strong Electrolytes Weak Electrolytes
 Degree of dissociation  Degree of dissociation
is high is low

 Electrical conductance  Electrical conductance

is good is poor

 Common examples are  Common examples are

ionic salts strong acids and bases
 Some electrolytes are considered to be
intermediate, whose characteristics are between
those of strong and weak electrolytes.

 Examples are weak acids and bases.

 Electrolytescan be classified according to the
charges of the cation and ion.

Electrolyte Cation Charge Anion Charge Example

1-1 +1 -1 NaCl, KBr
1-2 +1 -2 Na2CO3, K2SO4
2-1 +2 -1 CaCl2, Ba(NO3)2
2-2 +2 -2 MgCO3, CuSO4
1-3 +1 -3 K3PO4
3-1 +3 -1 Fe(NO3)3
2-3 +2 -3 Ca3(PO4)2
3-2 +3 -2 Fe2(SO4)3
 Strong electrolytes are ionic substances, and
dissolve completely in water.
 The electrical environment of a strongly electrolytic
solution is measured by the Debye-Huckel Theory,
which provides a formula for the ionic strength:
1
𝐼 = ෍ 𝐶𝑖 𝑍𝑖2
2
What is the ionic strength in M of a
solution that is 0.2M in ferric sulfate?
What is the ionic strength in M of a
solution that is 0.1M potassium nitrate and
0.2M potassium sulfate?
 The presence of electrolytic solutes, whether strong
or weak, affects some of the properties of the pure
solvent. These are called colligative properties, and
are as follows:
1. Boiling point elevation
2. Freezing point depression
3. Vapor pressure lowering
4. Osmotic pressure
 The boiling point of an electrolytic solution is higher
than that of the pure solvent.
∆𝑇𝑏 = 𝑖𝑘𝑏 𝑚
 kb is the ebullioscopic constant. For water, the
ebullioscopic constant is 0.513 K/m.
 The freezing point of an electrolytic solution is
lower than that of the pure solvent.
∆𝑇𝑓 = 𝑖𝑘𝑓 𝑚
 kf is the cryoscopic constant. For water, the
ebullioscopic constant is 1.86 K/m.
 Thevapor pressure of a liquid solvent in solution is
lower than that of the pure liquid.
∗ ∗
𝑃𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝑥𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑃𝑠𝑜𝑙𝑣𝑒𝑛𝑡
 Osmotic pressure is the pressure that must be
exerted on a solution to prevent fluid flow when a
semipermeable membrane separates the solution
from a pure solvent.
𝜋 = 𝑖𝑀𝑅𝑇
 If the solvent is not water and the ebullioscopic
and/or cryoscopic constants are unknown, the
following formula can be used:
𝑅𝑇 2 𝑀𝑊
𝐾=
∆𝐻
 ΔH is the latent heat of transition (fusion for the
cryoscopic constant, vaporization for the
ebullioscopic constant).
 Note: for the ebullioscopic constant, if ΔHvap is not
given, the T.H.E. rule can be applied.
 It is used to measure the effect of a solute on the
colligative properties of a solution.
 It is the ratio between the actual concentration of
particles produced when the substance is dissolved,
and the concentration of a substance as calculated
from its mass.
 It
can be used to measure the degree of dissociation
of a weak electrolyte. From Arrhenius Theory:
𝑖−1
𝛾=
𝑣−1

 From Debye-Huckel Theory:

𝑖 = 𝑣 1 − 0.375 𝑧+ 𝑧− 𝐼
The boiling point of water at 749.2 mm Hg
is 99.60˚C. What mass percent of sucrose
(342) should be present in an aqueous
sucrose solution to raise the boiling point
to 100˚C at this pressure?
An aqueous solution at 26.85˚C of 0.72% by
weight HCl freezes at -0.706˚C.
a. Calculate the Van’t Hoff factor i.
b. Calculate the osmotic pressure of the
solution in mmHg.
c. Calculate the boiling point of the
solution in ˚C.
A 0.1m solution of a weak electrolyte
ionizing into two ions freezes at -0.208˚C.
Calculate the degree of dissociation.
An aqueous solution of urea freezes at –
4.65˚C. Calculate the freezing point of a
solution prepared by diluting 150 grams of
this solution with 50 grams of water.
The vapor pressure of water at 25˚C is
23.756 torr. A solution consisting of 18.913
grams of a non-volatile substance in 36
grams of water has a vapor pressure of
20.234 torr. What is the molecular weight
of the solute?
150g of NaCl is dissolved in 300g of diethyl
ether. The boiling point elevation of the
solution is 26K. Normal boiling point of diethyl
ether is 34.6˚C.
a. Assuming that the Trouton-Hildebrand-
Everett Rule applies, compute for the
ebullioscopic constant KB.
b. Compute for the Van’t Hoff factor.
c. Compute for the degree of dissociation (%).
Using the Debye-Huckel Theory, calculate
the Van’t Hoff factor for a 0.04M solution
of potassium phosphate.
 States that during electrolysis, the amount of
chemical reaction which occurs at any electrode
under the influence of electrical energy is
proportional to the quantity of electricity passed
through the electrolyte.
𝑄 = 𝐼𝑡 = 𝑛𝐹
A constant current was passed through a
solution of CuSO4 for 1hr and 0.04g of
copper was deposited. What is the
current?
A technician is plating a faucet with 0.86 g
of chromium from an electrolytic bath
containing aqueous Cr2(SO4)3. If 12.5 min is
allowed for the plating, what current is
needed? The atomic mass of Cr is
52.00amu.
What mass of magnesium (24.31) is
produced when 100,000 A is passed
through a MgCl2 melt for 1 hour if the yield
of magnesium is 85%?
Three electrolyte cells A, B, and C
containing solution of ZnSO4, AgNO3, and
CuSO4, respectively are connected in
series. A steady current of 1.5A was passed
through them until 1.45g of silver
deposited at the cathode of cell B. How
long did the current flow? What mass of
copper was deposited?
What quantity of electricity would be
required to reduce 10 g of nitrobenzene,
C6H5NO2, completely to aniline, C6H5NH2
(reaction below)? If the potential drop
across the cell is 2 volts, how much
energy, in calories, is consumed in the
process?
+ −
𝐶6 𝐻5 𝑁𝑂2 + 6𝐻 + 6𝑒 → 𝐶6 𝐻5 𝑁𝐻2 + 𝐻2 𝑂
 The Nernst Equation enables the determination of
cell potential under non-standard conditions. It
relates the measured cell potential to the reaction
quotient and allows the accurate determination of
equilibrium constants.
𝑅𝑇 °
𝐸=𝐸=𝐸 − 𝑙𝑛𝐾
𝑛𝐹
For the overall reaction at standard
conditions: Sn(s)+Pb2+(aq)→Sn2+(aq)+Pb(s),
a. What is the value of E˚cell?
b. What is the standard Gibbs energy
change of the reaction?
c. What is the equilibrium constant, K?
Assume that you have a cell that has an
iron (III) concentration of 0.015M and an H+
concentration of 1x10-3M. The cell
temperature is 38˚C. What would the cell
potential be under these conditions?
Suppose that we wish to study the possible
galvanic corrosion between zinc and
chromium. What is the chemical reaction
that takes place and what is the standard
free energy change for that reaction?
Calculate the EMF at 25˚C of the cell
Pt|Sn2+(0.1m),Sn4+(0.01m)||Fe3+(0.5m)|Fe
given that: Fe3++3e-→Fe, E˚=-0.041V;
Sn4++2e-→Sn2+, E˚=0.151V.
Physical Chemistry for Engineers 2 Lecture
Rey Martin G. Estoque
Adamson University
Chemical Engineering Department