Chemical Engineering Calculations

Problem Set 6 - MATERIAL BALANCE WITH CHEMICAL REACTIONS

NAME ___________________________________

1. The successive reactions in the manufacture of HCI from salt and sulfuric acid may be represented by the
following equations:
NaCl + H2SO4 = NaHSO4 + HCI
NaCI + NaHSO4 = Na2SO4 + HCl
In practice the salt is treated with aqueous sulfuric acid containing 75% H2SO4 in slight excess of the
quantity required to combine with all the salt to form Na2SO4. Although the first reaction proceeds readily,
strong heating is required for the second. In both steps, the process HCl and water vapor are evolved from
the reaction mass. "Salt Cake" prepared by such a process was found to have the following composition:
91.48% Na2SO4, 4.79% NaHSO4, 1.98% NaCl, 1.35% H2O and 0.4% HCl. The salt used in the process is dry
and may be assumed to be pure NaCl. On a basis of 1000 kg of salt charged.
Calculate:
(a) weight of acid added, weight of salt cake formed and weight of each gas driven off
(b) % conversion of NaCl in the first reaction and the degree of completion of the second reaction.

2. Phosphorus is prepared by heating in the electric furnace a thoroughly mixed mass of calcium phosphate,
sand and charcoal. It may be assumed that in a certain charge the following conditions exist: the amount of
silica used is 10% in excess of that theoretically required to combine with the calcium to form the silicate;
the charcoal is 40% in excess of that required to combine, as carbon monoxide, with the O2 that would
accompany all the phosphorus as the pentoxide.
Calculate:
(a) the % composition of the original charge
(b) the kg of P obtained per 100 kg of charge, assuming that the decomposition of 
the phosphate
by the silica is 90% complete and that the reduction of the liberated oxide of 
P, by the carbon,
is 70% complete.

3. In the Deacon Process for the manufacture of Cl2, a mixture of HCI gas and air is passed over a heated
catalyst which promotes oxidation of the acid. Air is used in 30% excess of that theoretically required.
(a) calculate per kg of acid, the kg of air supplied,
(b) mass composition of the gas mixture entering the reaction chamber and
(c) wt% composition of the gases leaving the chamber assuming 60% of the acid is oxidized.

4. In order to obtain barium in a form that may be put into solution, the natural sulfate, barytes, is fused
with sodium carbonate. A quantity of barytes, containing only pure barium sulfate and infusible matter, is
fused with excess pure, anhydrous soda ash. Upon analysis of the fusion mass it is found to contain 11.3%
BaSO4, 27.7% Na2SO4 and 20.35% Na2CO3. The remainder is barium carbonate and infusible matter.
Calculate:
(a) % completion of the conversion of barium sulfate to carbonate and the analysis of the 
fusion
mass.
(b) Composition of the original barites
(c) % excess Na2CO3

5. In the Le Blanc Soda Process the first step is carried out according to the following reaction:
NaCI + H2SO4 = NaCI + NaHSO4 + HCI
The acid contains 80% H2SO4. It is supplied 5% in excess of that theoretically required by the above reaction.
 (a) Calculate the weight of the acid supplied/1000 kg salt charged
(b) Assume the reaction goes to completion, and that in the process 90% of the HCI formed and
25% of the water present are removed, calculate the weights of HCI and water removed per
1000 kg of salt charged.
(c) Assuming conditions of (b), calculate the % composition of the remaining salt mixture.

6. In the common process for the manufacture of nitric acid, sodium nitrate is treated with aq. sulphuric
acid containing 95% H2SO4. In order that the resulting "niter cake" may be fluid; it is desirable to use
sufficient acid so that there will be 34% H2SO4 by wt in the final cake. This excess H2SO4 will actually be in
combination with the Na2SO4 in the cake, forming NaHSO4, although for purposes of computation it may be
assumed to be free acid. The cake will contain 1.5% water and the reaction will go to completion, but 2% of
the HNO3 formed will remain in the cake. Assume that the NaNO3 used is dry and pure. Calculate per 100 kg
of NaNO3 charged:
(a) wt and % composition of the niter cake
(b) wt of aqueous acid to be used
(c) wt of water vapor and nitric acid distilled from the niter cake.

7. Pure CO2 may be prepared by treating limestone with aqueous sulfuric acid. The limestone used
contained CaCO3, MgCO3 and inerts. The acid used contained 12% H2SO4. The residue from the process had
the following composition: 8.56% CaSO4, 5.23% MgSO4, 1.05% H2SO4, 0.53% inerts, 0.12% CO2 and the rest
water. During the process the mass was warmed and CO2 and water vapor were removed. Calculate:
(a) Analysis of the limestone
(b) % excess acid used
(c) wt and analysis of the material distilled from the reaction mass per 1000 kg of limestone
treated.

8. Barium carbonate is commercially important as a basis for the manufacture of other barium compounds.
In its manufacture, barium sulfide is first prepared by heating the natural sulfate, barytes with carbon. The
barium sulfide is extracted from this mass with water and the solution treated with sodium carbonate to
precipitate the carbonate of barium. In the operation of such a process it is found that the solution of
barium sulfide formed contains also some calcium sulfide, originating from impurities in the barytes. The
solution is treated with sodium carbonate, and the precipitated mass of calcium and barium carbonates is
filtered off. It is found that 16.45 kg of dry precipitate are removed from each 100 kg of filtrate collected.
The analysis of the precipitate is: 9.9% CaCOs and 90.1% BaCO3. The analysis of the filtrate is 6.85% Na2S,
2.25% Na2CO3 and 90.9% H2O. The sodium carbonate for precipitation was added in the form of anhydrous
soda ash which contained CaCO3 as an impurity. 
Calculate:
(a) % excess Na2CO3 used above that required to precipitate BaS and CaS
(b) Composition of the original solution of Barium and calcium sulfides
(c) composition of the dry soda ash used in the precipitation

9. Chlorobenzene is nitrated using a mixture of nitric acid and sulfuric acid. During the pilot plant studies, a
charge consisted of 100 kg of chlorobenzene, 106.5 kg of 65.5% by wt nitric acid and 108 kg of 93.6% by wt
sulfuric acid. After 2 hours of operation, the final mixture was analyzed. It was found that the final product
contained 2% unreacted chlorobenzene. Also the product distribution was found to be 66% p-
nitrochlorobenzene and 34% 0- nitrochlorobenzene. Calculate:
(a) % conversion of chlorobenzene and 
 (b) composition of the product mixture.
10. Dehydrogenation of ethanol is a commercial process of manufacturing acetaldehyde. Pre-mixed

ethanol-air mixture was passed over a silver catalyst The content of ethanol in the mixture was 
found to
be 2 kg ethanol per kg of air. The reactions taking place in the reactor are as follows:
CH3CH2OH = CH3CHO + H2
2 CH3CH2OH + O2 = 4 CO + 6 H2 
2 CH3CH2OH + 3 O2 = 4 CO2 + 6 H2 
2 CH3CH2OH + 2 H2 = 4 CH4 + O2
2 H2 + O2 = 2 H2O
The gases from the converter were passed through a scrubber where cold, dilute alcohol cools the gases
and dissolves both the alcohol and acetaldehyde. The stripped gases leaving the scrubber were scrubbed
again with water in the second scrubber and released to the atmosphere. The dilute alcohol-acetaldehyde
solution from the bottom of the first scrubber was sent to a distillation tower to produce 99% pure
acetaldehyde as an overhead product. The gases leaving the second scrubber were analyzed contain 0.7%
CO2, 2.1% O2, 2.3% CO, 7.1% H2, 2.6% CH4 and 85.2% N2 on a dry basis by volume. Find:
(a) the conversion of ethanol in the converter
(b) the yield of acetaldehyde.

11. A pilot plant reactor was charged with 50 kg naphthalene and 200 kg (98% by wt) H2SO4. The reaction

goes to 90% completion. The product distribution was found to be 18.6% monosulfonate naphthalene
and 81.4% disulphonate naphthalene. Calculate the complete analysis of the product.

12. Commercial hydrochloric acid and sodium sulfate are produced by the reaction:
NaCI + H2O + SO3 = Na2SO4 + HCI
The reaction is carried at 4820C. After separation of the Na2SO4, the HCI is to be absorbed in water. Per
1000 kg of sodium chloride charged, how much Na2SO4 and 87% by wt aqueous hydrochloric acid solution
are obtained if the reaction goes to 90% completion? If the SO3 is supplied 20% in excess and H2O, 100 % in
excess of the theoretical amount, how much 98% sulfuric (SO3and H2O) and fresh water should be fed to
the reactor?

13. Calcium carbide is manufactured from limestone and coal:

CaCO3 = CaO + CO2
CaO + C = CaC2 + CO
Limestone containing 91 % CaCO3 and 9% inerts is available. The first reaction is 95% complete while the
second is 90% complete. 4.8 MT of limestone, 4.86 MT of coal containing 80% C and 20% ash are available.
Find the amount and composition of the solid and gaseous products.

14. An alkaline solution of sodium carbonate made up of 0.594% NaOH, 14.88% Na 2CO3 and 84.53% water
is causticized by the addition of partly slaked lime. The lime contains CaCO3, CaO and Ca(OH)2.' The mass
obtained from the causticization has the following analysis: 13.48% CaCO3, 0.28% Ca(OH)2, 0.61% Na2CO3,
10.36% NaOH and the rest is water. The reactions are:
CaO + H2O = Ca(OH)2 
Na2CO3 + Ca(OH)2 = NaOH + CaCO3
On a basis of 100 kg of the caustlclzed mass, calculate:
(a) Wt and composition of the lime
(b) Wt of the alkaline liquor
(c) % excess reactant
(d) degree of completion of the overall reaction

15. Phosphoric acid is made by reacting the rock phosphate with hydrochloric acid. It is desired to use the
rock phosphate, obtained from the hilly area near Montalban. The composition of the rock phosphate is as
follows: 34.55% P2O5, 48.62% CaO,3.76% Al2O3and Fe2O3, 1.29% MgO, 5.58% SiO2, 2.5% CaF2, 1.3% CO2 and
2.4% SO3. The laboratory tests reveal the following data: 25% by wt HCI used = 3.0 kg per kg rock
phosphate. Water retention in the sludge = 0.22 kg water per kg rock phosphate. P2OS retained in the
sludge = 2%. It is intended to make 2 tonnes/h of phosphoric acid of 80% strength. Assume that: (i) 95% of
the P2O5 present in the rock is reacted; (ii) all CaF2 takes part in the reaction, (iii) the recovery of H3PO4 is
87% by leaching process (using butyl alcohol). The main reaction is:
Ca3(PO4)2 + HCI = H3PO4 + CaClz
Side reactions are:
CaF2 + HCl = HF + CaCl2
HF + SiO2 =H2SiF6 + H2O
Calculate:
(a) the % excess acid used
(b) the quantity of rock phosphate to be treated per hour
(c) the quantity of CaCl2 formed per hour

16. A blast furnace is to be used to produce pig iron. The iron ore used contains 90% Fe 2O3, 5% FeO, 3%
SiO2 and 2% Al2O3 . The fuel used is coke containing 90% C, 3 % CaO, 2% MgO and 5 % SiO2. A fluxing agent
is added which is limestone that analyzes 95% CaCO3, 3% MgCO3 and 2% SiO2. The coke rate is 1 tonne per
tonne of pig iron. The pig iron product contains 4% C, 1% Si and the rest is Fe. A slag is also formed which
contains 45% CaO, MgO, Al2O3 and SiO2.The following is the complete analysis of blast furnace gas by
volume (volume%=mole%): 16.5% CO2, 9%CO, 7.0%O2, 6.0% H2O and the rest is N2. Assume that no FeO is
present in the slag. For 1 tonne of pig iron production, calculate the weight of limestone, ore, and slag.
Determine the volume of wet air in m3, if air is supplied at 50oC and 100 kPa.

17. The catalytic reforming of methane with steam at high temperature and atmospheric pressure is one
way to prepare hydrogen for the production of NH3:
CH4(g) + H2O(g) CO(g) + 3 H2(g)
Other reaction: CO(g) + H2O(g) CO2(g) + H2(g)

If you begin with 990 kg of CH4 and 2300 kg of H2O and you obtain 430 kg of H2 and 2080 kg of CO2 at 400oC
and 1 atm, calculate the total volume of the gas collected after the reactions.