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Tutorial 5

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10 views

Tutorial 5

Uploaded by

I RAJ
Copyright
© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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TUTORIAL SHEET- 5 (PHYSICAL CHEMISTRY)

Electrochemistry

1. The emf of a cell corresponding to the reaction:


Zn( s ) + 2 H + (aq ) ↔ Zn 2+ (0.1M ) + H 2 ( g ) EZn+ / Zn ° = 0.76V
at 1atm is 0.28V at 15°C . Write the half – cell reaction and calculate the pH of solution at the
hydrogen electrode.

2. Two half-cell reactions may be combined in such a way as to form a) a new half-cell reaction or b)
a complete cell reaction. Illustrate both a) and b) by using the half cell reactions listed below and
calculate E˚ values for both the new half-cell and complete cell reactions.
i) 2 H 2 O(l ) + 2e − → H 2 ( g ) + 2OH − (aq ) E˚ = -0.828V
+ −
ii) Ag (aq ) + e → Ag ( s ) E˚ = +0.799 V

3. The standard emf of the cell: Pt ( s ) | H 2 (1atm), H + (a = 1) || KCl (aq., a = 1) | AgCl ( s ) | Ag ( s )


at 298 K is 0.223 V. The temperature coefficient of emf at constant pressure -0.65mV K-1
(a) Write the cell reaction. (b) Calculate ΔH˚, ΔG˚, ΔS˚ for the reaction.

4. From the following data estimate the value of equilibrium constant for the reaction:
Cu + Cu 2+ + 2Cl − ↔ 2CuCl ( s )
°
Given: ECu 2+
/ Cu
= 0.34V ; ECu
°
2+
/ Cu +
= 0.15V and solubility product of CuCl, K SP = 3.2 × 10 −7

5. The standard cell potential of: Pt/H2(g)/HBr(aq)/AgBr(s)/Ag(s)


was measured over a range of temperatures, and the data were fitted to the following polynomial:
E∅/V = 0.07131 - 4.99×10-4(T/K-298) – 3.45× 10-6 (T/K-298)2. Evaluate the standard reaction
Gibbs energy, enthalpy, and entropy at 298 K.

6. A hydrogen electrode and a calomel half cell are used to determine pH of a solution on a mountain
top where the pressure is 500 mm of Hg and temperature 25oC. The pressure was wrongly assumed to
be 760 mm of Hg and the pH was found to be 4. What is the correct pH? [Hints: the cell is
H2(P)/solution// KCl, Hg2Cl2/ Hg ]

7. Calculate equilibrium constant of disproportion reaction


2Cu + (aq ) → Cu 2+ + Cu ( s )

The standard electrode potentials are E °Cu+ / Cu =


0.52 V ; E °Cu 2+ / Cu + =
0.16 V . Comment on your
results.
8. The thermodynamic dissociation constant for acetic acid, HAc, is 1.75 × 10-5 at 250C. Calculate
using the Debye-Huckel theory, the degree of dissociation of 0.001(M) acid in 0.05(M) Ca(NO3)2.
[Given, A= 0.51]

9. The standard electrode potentials of the electrodes Cu2+/Cu and Ag+/Ag are 0.337 V and 0.7991 V.
What would be the concentration of Ag+ in a solution containing 0.06 M of Cu2+ ion such that both
the metals can be deposited together? Assume that activity coefficients are unity and both silver and
copper do not dissolve among themselves.

10. The EMF of the cell Cd(s), CdCl2 (m = 0.02) | AgCl (s), Ag(s) is found to be 0.780V at 25
0
C. Using the standard potentials, viz., E°Cd 2+ / Cd = -0.403 V and E°AgCl / Cl- = +0.222 V , Calculate the

mean ionic activity coefficient of CdCl2 at this temperature.

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