A.

ELECTROCHEMICAL CELLS
1. A lead-lead ion electrode is measured against a 0.1 N calomel electrode at 25 C. The lead
electrode is found to be negative, and the observed emf is 0.4603 volt. Write the cell reaction
and calculate the potential of the lead-lead ion electrode.

@ 25 ℃, ƐC = 0.33V of a 0.1N calomel electrode.

Pb(s) = Pb2+(a = 1) + 2e-
Hg2Cl2(s) + 2e- = 2Hg(l) + 2Cl-(0.1N)
ƐCell = ƐPb + ƐC
0.4603 volt = ƐPb + 0.33 volt
ƐPb = 0.1303 volt
2. A silver-silver ion electrode is measured against a normal calomel electrode at 25 C. The calomel electrode
is negative, and the observed emf is 0.2360 volt. Write the cell reaction and calculate the potential of the
silver-silver electrode.

Ag2+(a = 1) + 2e- = Ag(s)

2Hg(l) + 2Cl-(1N) = Hg2Cl2(s) + 2e-
ƐCell = ƐAg + ƐC
0.2360 volt = -0.2800 volt + ƐAg
ƐAg = 0.516 volt
3. Suppose that the lead electrode in problem 1 is coupled with silver electrode in problem 2. (a) What will
be the cell reaction? (b) Which electrode will be negative? (c) What will be the emf of the cell?

a.) Pb(s) + Ag2+ +(a = 1) + 2e- = Pb2+(a = 1) + 2e- + Ag(s)

b.) The lead electrode will be negative
c.) ƐCell = ƐAg + ƐPb = 0.516 volt + 0.1303 volt =0.6463 volt
4. In each of the following cells write the cell reaction, and designate which reactions
are spontaneous as written.

Solution:

a) 2Ag + Cl- + I- (s) → AgCl(s) +AgI (s) ; SPONTANEOUS

b) K + Hg2Cl2 (s) → K+ +2Cl- + 2Hg; NON-SPONTANEOUS
c) Tl+(aq) + Cu2+ (aq) → Tl3+ (aq) + Cu (s) ; NON-SPONTANEOUS
d) Ni + Pb2+ → Ni2+ +Pb; SPONTANEOUS
B. PHASE RULE
1. Give the number of components in the following systems:
(a) water, allowing for its autoprotolysis,
2H2O ⇌ OH−+ H3O+
C=N–E
Where: C = number of components
N = Number of species in the system
E = number of independent equations
C=3–1=2
(b) aqueous acetic acid,
CH3COOH(aq)
C=2
(c) magnesium carbonate in equilibrium with its decomposition products.
MgCO3 → MgO + CO2
C=N–E
C=3–1
C=2
2. A. State how many components are present in each; and
B. how many degrees of freedom for each of the following systems:
a. NH3(g)
C=1
F=2+C–P
Where C is the number of chemical species, and P is the number of phase present in the system.
F=2+1–1
F=2
b. An aqueous solution of NaCl + Na2SO4
C=3
F=3–2+2
F=3
c. An aqueous solution of KCl + Na2SO4
C=3
F=3–2+2
F=3
3. How many degrees of freedom will each of the following systems?
a. NaCl(s) in equilibrium with its saturated solution at 25 °C and 1 atm pressure
F=C–P+0
F=2–3+0
F=-1
b. the I2 (s) in equilibrium with its vapor at constant T (50°C)
F=1–2+1
F=0
c. HCl(g) + NH3(g) in equilibrium with NH4Cl(s) when the equilibrium is approached by starting with the two gases only
C=1
F=1–2+2
F=1
d.HCl(g) + NH3(g) in equilibrium with NH4Cl(s) when the equilibrium is approached by starting with the solid.
C=2
F=2–2+2
F=2
4. Suppose that a one component system exhibits a gas phase,a liquid phase and three solid modification. How
many one−,two−,three,and four −phase equilibria are possible in the system?

F= C-P+2
@Eqbm ; F= 0; no. of compounds =1

0=1-P+2 ;
P= 3 (SOLID, LIQUID, GAS)
.: at triple point.