Industrial Processes

I. NH3 – Haber Process

finely divided Fe
1. N2(g) + 3H2(g) 2NH3(g)
450 C, 200 atm
2. Conditions
a. Pressure (200 atm)
Higher: favours FR,  [] (reaction rate)
Not very high: safety, construction & maintenance cost
b. Temperature (400 – 450 °C)
Lower: favours FR
Not very low: reaction rate
c. Catalyst (finely divided Fe)
 reaction rate,  time for reaching eqm
finely divided:  surface area (& catalytic activity) (surface adsorption)

II. HNO3 / NH4NO3 – Ostwald Process

Pt - Rd
1. 4NH3(g) + 5O2(g)   4NO(g) + 6H2O(g)
900 C, 8 atm
2. 2NO(g) + O2(g)  2NO2(g)
OR
3A. 4NO2(g) + O2(g) + 2H2O(l) 40 C
3B1. 2NO2(g) N2O4(g)
 4HNO3(aq) 7  12 atm
3B2. 3N2O4(g) + 2H2O(l)
 4HNO3(aq) + 2NO(g)
170  180 C
4. HNO3(aq) + NH3(aq)   NH4NO3(aq)
4 atm
5. Considerations in fertilizer production
a. NH3 is toxic – throat irritation, eye injury, inability to breathe
b. explosion, fire hazards
c. stored in liquid form
d. low equipment cost
e. through pipelines, tankers, rail, trucks
f. solid stored in dry places (prevent cake formation)
g. protected from sunlight
h. excessive use: emission of NOx (greenhouse gas), pest problem
III. Cl2 / H2 / NaOH – Chloro-alkali industry
1. 2Cl–(aq)  Cl2(aq) + 2e– (Anode)
2. 2H+(aq) + 2e–(aq)  H2(g) (Cathode – Membrane cell)
3. Na+(aq) + e–  Na(l) (Cathode – Hg Cell)
4. Na(l) + Hg(l)  Na/Hg(l) (Hg cell)
5. 2Na/Hg(l) + 2H2O(l)  2NaOH(aq) + 2Hg(l) + H2(g) (Hg cell)

IV. CH3OH
NiO
1. CH4(g) + H2O(g) CO(g) + 3H2(g)
850 C, 10  20 atm
(Steam reforming, syngas production)
Cu / ZnO / Al2O3
2. CO(g) + 2H2(g) CH3OH(g)
250 C, 50  100 atm
3. Uses
a. feedstock of chemical products (e.g. methanol, ethanoic acid)
b. energy sources (fuel cells, liquid fuel in car engine)
c. solvent in producing pharmaceuticals

V. CH3COOH
A. Fermentation
fermentation  CH CH OH 
Sugar  oxidation  CH COOH
3 2 3

B. Oxidation of naphtha / butane

180 C, 55 atm  4CH COOH + 2H O
C4H10 + O2  3 2
(CH3COO )2 Co2
C. Wacker process (oxidation of ethene)
PdCl2 / CuCl2 [O]
CH2=CH2 + H2O   CH3CHO   CH3COOH

D. Monsanto process (Carbonylation of methanol)

Rh / I
CH3OH(l) + CO(g)  CH3COOH(l)
150  200 C, 30  60 atm
E. Cativa process

CH3OH(l) + CO(g) Ir CH3COOH(l)

150  200 C, 30  60 atm