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Chemists Daily Chapter 18-1

1. Assign oxidation numbers to each atom in: NiCl2 Nickel ion charge would be +2, so oxidation number is +2

Chloride ion charge would be 1, so each chlorine has an ox # of -1

Mg2TiO4

Oxygen ox # (from the rules) is -2

Magnesium ion charge would be +2, so oxidation number is +2

Titanium ox # of +4, so that the whole thing adds up to zero charge Oxygen ox # (from the rules) is -2

K2Cr2O7

Potassium ion charge would be +1, so oxidation number is +1

Chromium ox # of +6, so that the whole thing adds up to zero charge

HPO4-

Oxygen ox # (from the rules) is -2

Phosphorus ox # of +6, so that the whole thing adds up to 1 charge 2. Identify whether each reaction is a redox reaction. If so, identify the oxidizing agent,

Hydrogen ox # (from the rules) is +1

the reducing agent, the substance being oxidized, and the substance being reduced. Zn (s) + 2HCl (aq) ZnCl2 (aq) + H2 (g)

a.

Product ox # Zn is +2, H is 0, Cl is 1

Reactant ox # Zn is 0, H is +1, Cl is -1

was oxidized and is the reducing agent. reduced and is the oxidizing agent b. Cr2O7
2-

Since there is a change in ox #, this is a redox reaction.

Since hydrogens ox # decreased, it was

Since Zns ox # inceased, it

Product ox # Cr is +6, O is -2, H is +1

Reactant ox # Cr is +6, O is -2, H is +1

(aq)

2OH- (aq)

CrO4

2-

(aq)

H2O (l)

Since there is no change in ox #s, this is not a redox reaction Identify the substances oxidized and reduced in the reaction of calcium and chlorine to What are the oxidizing and reducing agents? + Cl2 CaCl2

3.

form calcium chloride.

Product ox # Ca is +2, Cl is 1 oxidizied)

Reactant ox # Ca is 0, Cl is 0

Balanced equation:

Ca

So oxidizing agent is Cl (which is reduced) and the reducing agent is Ca (which is

Chemists Daily Chapter 18-2

CH3OH (aq)

1. Balance the following equations: + Cr2O7


2-

CH3OH CH2O

Write half reactions:

(aq)

CH2O (aq)

Cr

3+

(aq)

in acidic solution
3+

Balance (not H or O) CH3OH CH2O Balance O using H2O CH3OH CH2O

Cr 2O7 Cr 2O7 Cr 2O7


+

2-

Cr

2-

2Cr

3+

2-

Balance H using H+

2Cr

3+

+ 7 H2 O 2Cr
3+

CH3OH CH2O + 2H

CH3OH CH2O + 2H + 2e+

Balance charge using eMake e- the same

14 H 14 H 14 H
3+

+ Cr2O7 + Cr2O7 + Cr2O7

2-

+ 7 H2 O
3+

2-

+ 6e- 2Cr

+ 7 H2 O + 7 H2 O

3CH3OH 3CH2O + 6H + 6e+

2-

Add and cancel 3CH3OH + 8 H


-

+ 6e- 2Cr

3+

+ Cr2O7 +

2-

3CH2O + 2Cr

+ 7 H2 O

Cl2 (g) Cl (aq) Cl2 Cl


-

Write half reactions: Balance (not H or O)

ClO (aq)

in basic solution Cl2 ClO


-

Balance O using H2O Cl2 Balance H using H+ Cl2 Balance charge using eMake + 2e- 2Cl
-

Cl2

2Cl

Cl2 2ClO

2Cl

Cl2 + 2H2O 2ClO

2Cl

Cl2 + 2H2O 2ClO + 4H


-

Cl2

Add and cancel

They are

e- the same

Cl2 + 2H2O 2ClO + 4H + 2e+

2Cl2 + 2H2O 2Cl + 2ClO + 4H


-

Cancel H2O

4 OH- + 2Cl2 + 2H2O 2Cl + 2ClO + 4H2 O


-

Make H2O from H

4 OH- + 2Cl2 + 2H2O 2Cl + 2ClO + 4H


+

Add 4 OH- to each side

and OH-

+ 4 OH-

4 OH- + 2Cl2 2 OH- + Cl2

Reduce coefficients
-

2Cl + 2ClO + 2H2O


-

Cl + ClO + H2O

Chemists Daily Chapter 18-3

1. G iven the following cell notation: Cr (s) | Cr


3+

(aq)

||

Cu

2+

(aq)

Cu (s)

Write a balanced equation for the cell reaction and give a brief description of the cell. The anode is first: Cr (s) Cr
2+ 3+

The cathode is second: 2Cr (s) 3Cu


2+

Make the number of electrons the same and add the reactions to get: (aq) + 2Cr
3+

Cu

(aq)

+ 2e-

(aq)

+ 3e-

Cu (s)

+ 6e-
2+

(aq)

3Cu (s)

+ 6e-

2Cr (s)

3Cu

(aq)

2Cr

3+

(aq)

+ 3Cu (s)
3+

The cell is a chromium anode dipped into a solution of Cr salt bridge. cathode dipped into a solution of Cu
2+

ions.

The two solutions are connected by a

ions and a copper

2. W rite the shorthand notation for a galvanic cell that uses the reaction: Mg (s) + Fe
2+

(aq)

Mg

2+

(aq)

Fe (s)

Splitting into half reactions: Mg (s) Fe


2+

So Mg is oxidized (this is the anode) and the Fe is reduced (this is the cathode). Mg (s) | Mg
2+

(aq) + 2e- Fe (s)

Mg

2+

(aq)

2e-

(aq) || Fe

2+

(aq) | Fe (s)

Chemists Daily Chapter 18-4

1. A galvanic cell consists of a Mg electrode in a 1.0 M Mg(NO3)2 solution and a Ag electrode in a 1.0 M AgNO3 solution. Calculate the E for this cell.

The reduction potentials are: E (Ag /Ag)


+

E (Mg

2+

/Mg)

0.80 V

-2.37 V

Silver has the more positive reduction potential, so it will be reduced. So Ecell = EAg+/Ag EMg2+/Mg = 0.80 (-2.37) = 3.17 V

2. a.

Determine whether the following reactions are spontaneous as written: 2Al


3+

6I

3I2

2Al

Since E is negative the reaction is NOT spontaneous b. 3Fe Fe


2+ 2+

So Ecell

Al is reduced, I- is oxidized. = EAl3+/Al EI2/I-

(-1.66) (+0.54) = -2.20 V

2NO

4H2O

3Fe

2NO3

8H

Since E is negative the reaction is NOT spontaneous c. Cr 3Ca


3+

So Ecell

is reduced, NO is oxidized. = EFe2+/Fe -

ENO3-/NO =

(-0.45) (+0.96) = -1.41 V

2Cr

3+

2Cr

3Ca

2+

So Ecell

is reduced, Ca is oxidized. = ECr3+/Cr ECa2+/Ca

Since E is positive the reaction is spontaneous

(-0.74) (-2.87) = +2.13 V

Chemists Daily Chapter 18-5

1. A current of 0.452 A is passed through an electrolytic cell containing molten CaCl2 for 1.5 hours. formed at the electrode.
2+

Write the electrode reactions and calculate the quantity of products (in grams)

Cathode: Ca Anode:

2Cl- (l) Cl2 (g)

(l)

+ 2e- Ca (l) + 2e-

1.50 hours x (60 min/hr) x (60 sec/min) = 5.40 x 10 Charge = current x time
3

seconds

(2.44 x 10

Charge = 0.452 A x (5.40 x 10

C) x (1 mole e- / 96485 C) = 0.0253 mole e-

seconds) = 2.44 x 10 As = 2.44 x 10


3

Anode:

Cathode: 0.0253 mole e- x (1 mole Ca/2 mole e-) x (40.08 g/mol) = 0.507 g Ca 0.0253 mole e- x (1 mole Cl2/2 mole e-) x (70.906 g/mol) = 0.897 g Cl2

Using the half reactions:

2. A constant current is passed through an electrolytic cell containing molten MgCl2 for 18 hours. If 4.8 x 10
5

grams of Cl2 are obtained, what was the current (in amperes)? + 2e-

Anode:

1.31 x 10

4.8 x 10

2Cl- (l) Cl2 (g)


9

grams

C = 1.31 x 10

x (1 mole Cl2/70.906 g) x (2 mole e-/1 mole Cl2) x (96485 C/mol e-) =


9

As

18 hrs x (3600 sec/hr) = 6.48 x 10 1.31 x 10 3.


9

sec
4

As / 6.48 x 10

sec = 2.02 x 10

NaCl with a constant current of 30,000 A? obtained as a byproduct?


+

How many hours are required to produce 1000 kg of sodium by electrolysis of molten How many liters of Cl2 at STP will be

4.350 x 10 4.350 x 10

1000 kg Na x (1000 g / 1 kg) x (1 mol Na/22.99 g) x (1 mol e-/1 mole Na) =


4

Anode:

Cathode: Na

2Cl- (l) Cl2 (g) mole e-

(l)

+ e-

Na (l) + 2e-

4 9

4.197 x 10 4.350 x 10

As / 30,000 A = 1.399 x 10

mole e- x (96485 C / 1 mole e-) = 4.197 x 10


5

sec = 38.86 hrs

C = 4.197 x 10

As

mole e- x (1 mol Cl2 / 2 mole e-) = 2.175 x 10 STP: 1 atm and 273 K

mole Cl2

V =

PV = nRT

(2.175 x 10

mole) (0.082057 Latm/molK) (273 K) / 1 atm = 4.872 x 10

Chemists Daily Chapter 18-6

1. Calculate the standard free energy change and Kc for the following reaction at 25 C. Sn (s) + 2Cu
2+

(aq)

Sn

2+

(aq)

2Cu

(aq)

Half reactions: Oxidation: So Ecell = Sn

G = - 58 kJ (recall that C = J/V) Ecell = (RT/nF) (ln K) K = 6.4 x 10


9

G = -(2 mole e-) (96485 C/mole e-) (0.29 V)

G = -nFE

ECu2+/Cu+

Sn -

2+

ESn2+/Sn

+ 2e-

(0.16) (-0.14) = +0.29 V

Reduction:

2Cu

2+

+ 2e-

2Cu

ln K = nEcell / 0.0257 V = (2) (0.29 V) / 0.0257 V = 22.6

Note 0.0257 V is the result of RT/F for 25 C 2. Predict whether the following reaction would proceed spontaneously as written at 298 K: Co (s) + Fe
2+

Ecell

Oxidation: =

The half reactions: EFe2+/Fe -

Given that [Co

2+

] = 0.15 M and [Fe


2+

(aq) Co
2+

2+

] = 0.68 M

(aq)

Fe (s)

Co Co

E = Ecell (0.0257 V / n) ln Q Q = [Co


2+

ECo2+/Co

+ 2e=

(-0.45) (-0.28) = -0.17 V

Reduction: Fe

2+

+ 2e- Fe

From the overall reaction (recalling that pure solids do not appear in Q expression) E = (-0.17) (0.0257 V / 2) (ln 0.22) = -0.15 V ] / [Fe
2+

0.15 / 0.68 = 0.22

Since E is negative, the reaction is NOT spontaneous in the direction written 3. A galvanic cell was set up using the following reaction: Mg (s) + Cd
2+

(aq)

Mg

2+

(aq)

Cd (s)

this cell was measured to be 1.54 V. The half reactions: Ecell = ECd2+/Cd -

electrode was dipped into a solution of unknown Cd

The magnesium electrode was dipped into a 1.0 M solution of MgSO4 and the cadmium
2+

What is the Cd

2+

concentration.

concentration?

The potential of

Oxidation:

Mg Mg

2+

E = Ecell (0.0257 V / n) ln Q Q = [Mg


2+

EMg2+/Mg

+ 2e-

(-0.40) (-2.37) = +1.97 V

Reduction: Cd

2+

+ 2e- Cd

From the overall reaction (recalling that pure solids do not appear in Q expression) ] / [Cd
2+

1.0 / [Cd

2+