Chemical Thermodynamics and Chemical Equilibrium problems

1. Calculate the thermal effect at 1000 K and 1 atm. for the reaction:

2 CO CO2 + C

It is known:
Substance  H , kcal/mol Cp, cal/mol K
CO -26.4 6.6 + 1.2  10-3 T
CO2 -94.0 10.3 + 2.6  10-3 T – 2  105 (1/T2)
C 0 2.7 + 2.8  10-3 T – 1.3  105
(1/T2)

R:  H = - 42.45 kcal

2. Calculate the reaction heat at constant pressure and 659 C for NH3 synthesis:

1/2 N2 + 3/2 H2 NH3

knowing  H = -11000 cal and

Substance Cp, cal/mol K

N2 6.30 + 1.82  10-3 T – 3.45  10-7 T2
H2 6.88 + 6.60  10-3 T + 2.79  10-7 T2
NH3 5.92 + 8.96  10-3 T – 1.76  10-6 T2

R:  H = - 17030 cal

3. Calculate the thermal effect at 800 K and 1 atm. for the reaction:

SO2 + ½ O2 SO3

knowing  H = -23.46 kcal and

Substance Cp, cal/mol K

SO2 6.15 + 13.8  10-3 T
O2 6.15 + 3.10  10-3 T
SO3 3.60 + 36.30  10-3 T

R:  H = -20.51 kcal
4. Calculate the thermal effect at 1223 K and 1 atm. for the reaction:

Pb + H2S PbS + H2

knowing Ttop, Pb = 600 K;  H = 1224 cal/mol şi

Substance  H , kcal/mol Cp, cal/mol K

Pbs 0 5.72 + 2.08  10-3 T
Pbl 0 6.80
H2S -4.8 7.00 + 3.75  10-3 T
PbS -22.5 10.63 + 4.61  10-3 T
H2 0 6.65 + 0.69  10-3 T

R:  H = -20.082 kcal

5. Calculate the entropy variation for the transformation of one mole of ice at 0 C in
steam at 120 C. It is known:
Cp(l) = 18 cal/mol K
Cp(g) = 6.89 + 3.3  10-3 T – 3.4  10-7 T2 cal/mol K
 H = 1436 cal/mol,  H = 9720 cal/mol, ttop = 0 C and tvap = 100 C.

 
R: S =
() ( )
+∫ dT + +∫ dT
R: S = 37.3 cal/K

6. Caculate the entropy varioation for the transformation of one mole of iron from
0 C to 1600 C. It is known:

Fe Cp, cal/mol K
 4.13 + 6.38  10-3 T
 6.12 + 3.36  10-3 T
 8.4
 10.0
lq 8.1

Transformare → → →  → lq

Temperatura C 785 906 1405 1530
 H , cal/mol 370 210 110 3560

R : S = 18.26 cal/mol K
 7. Calculate the entropy variation at 1000 K and 1 atm for the reaction:

MnO2 + CO MnO + CO2

It is known:

Substance S , cal/mol K Cp, cal/mol K

MnO2 13.9 1.90 + 48  10-3 T – 29  10-6 T2
CO 47.3 6.60 + 10-3 T
MnO 14.4 7.40 + 10  10-3 T – 3  10-6 T2
CO2 51.1 10.3 + 3.0  10-3 T – 2  105 (1/T2)

R : S = 0,7 cal/K

8. For reaction A + 2B C + D calculate Kp, Kx, Kc and  G knowing that all

the substances are gases and the initialy mixture contained 2 moles of A and 2
moles of B. At equilibrium there are in the mixture 0.75 moles of C. The reaction
takes place at 298 K and 1 atm.

R : Kx = 5.096
Kp = 5.096 atm-1
Kc = 2.080 l/mol
 G = -4032.6 J/mol
 Chemical Kinetics problems

1. For the reaction : A +B C + D it is known c = 5 mol/L, c = 4 mol/L and

t1/2A = 20 min. After how long time the concentration of B substance is reduced to
a half ?

R: k2 = 0.014 L/mol min

t1/2B = 13 min

2. For the reaction of first order A Products the half life time is 20 min.
After how long time the reactant concentration become 3 mol/L. The initially
reactant concentration is c = 8 mol/L.

R: k1 = 0.035 min-1
t = 28 min

3. Calculate the half life time and the kinetic constant for a reaction of first order
A Products knowing that after 10 min the reactant concentration
decreased with 10%.

R: k1 = 0.01 min-1
t1/2B = 67.8 min

4. Calculate the kinetic constant and the half life time for a reaction of second order
2A Products knowing that after 30 min left not reacted 10% of A, and
the initially reactant concentration was.

R: k2 = 0.01 L/mol min

t1/2 = 3.33 min

5. There are the first order reactions:

A Products k = 0.05 min-1
B Products k = 0.02 min-1

Knowing c = 4 mol/L and c = 3 mol/L calculate after how long time B

concentration will be equal with A concentration if the two reactions take place
simultaneously.

R: t = 9.6 min