Principles ch.8 Dr. Hameed R.

Alamery

Material balances
Material balances:-
A material balance is nothing more than the application of the law of the conservation of
mass: "Matter is neither created nor destroyed."
Although the conservation of mass is a simple concept, detailed explanations are required
to enable you to be able to apply it to a full range of chemical engineering systems.

a. System.
The system is mean any arbitrary portion of or a whole process that you want to consider
for analysis, such as a reactor, a section of a pipe. or an entire refinery by stating in words
what the system is.

The second define the system by drawing the system boundary, namely a line that encloses
the portion of the process that you want to analyze.

b. Closed system.
Closed system that is the system not enters nor leaves the vessel. That is, no material
crosses-the system boundary.
Closed system. Changes can take place inside the system, but for a closed system,
((No mass exchange occurs with the surroundings)).
.‫هو النظام الذي ال يحدث تبادل للكتلة مع محيط‬
c. Open system.
Open system: (also called a flow system) is the system that is material crosses the system
boundary.
.‫ (يسمى أيضًا نظام التدفق) هو النظام الذي تعبرالمادة حدود النظام‬:‫النظام المفتوح‬

***PROCESS CLAASSFICATION-:

Accumulation: An increase or decrease in the material (e.g., mass or moles) in the

system.

Batch process: A process in which material is neither added to nor removed from the
process during its operation.

Closed system: A system that does not have material crossing the system boundary.

Component balance: A material balance on a single chemical component in a system.

Conservation or mass Matter is neither created nor destroyed overall.

Consumption: The depletion of a component in a system due to chemical reaction.

Continuous process: A process in which material enters and/or exist continuously.

1
 Principles ch.8 Dr. Hameed R. Alamery

Final condition: The amount of material (e.g., mass or moles) in the process at the end of
the processing interval.
Flow system: An open system with material entering and/or leaving.

Generation: The appearance of a component in a system because of chemical reaction.

Initial condition: The amount of a material (e.g. mass or moles) in the process at the
Beginning of the processing interval.

Input Material: (e.g., mass, moles) that enters the system.

Material balance: The balance equation that corresponds to the conservation of mass.

Negative accumulation: A depletion of material (usually mass or moles) in the system.

Open system: A system in which material crosses the system boundary.

Output: Material (e.g. mass, moles) that leaves the system.

Rate: Flow per unit.

Semi-batch process: A process in which material enters the system but product is not
removed during operation.

Steady-state system: A system for which all the conditions (e.g., temperature, pressure,
amount of material) remain constant with time.

System: Any arbitrary portion of or whole process that is considered for analysis.

System boundary: The closed line that encloses the portion of the process that is to be
Analyzed.

Transient system: A system for which one or more of the conditions (e.g., temperature,
pressure, amount of material) of the system vary with time. Also
known as an unsteady-state system.

Unsteady-state system: A system for which one or more of the conditions (e.g.,
temperature, pressure, amount of material) of the system vary
with time. Also known as a transient system.

2
 Principles ch.8 Dr. Hameed R. Alamery

Types of Material Balance Calculations:-

It is convenient to study material balance calculations by putting them in four separate

section:-
1- Material balances without chemical reactions.
2- Material balances with chemical reactions.
3- Material balance on combustion processes.
4- Material balance on processes involving Recycle, Bypass, and purge streams.

𝐼𝑁 − 𝑂𝑈𝑇 + 𝐺𝐸𝑁. − 𝐶𝑂𝑁𝑆. = 𝐴𝐶𝐶. 𝑢𝑛𝑠𝑡𝑎𝑑𝑦 𝑤𝑖𝑡ℎ 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝐼𝑁 − 𝑂𝑈𝑇 = 𝐴𝐶𝐶. 𝑢𝑛𝑠𝑡𝑎𝑑𝑦 𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝐼𝑁 = 𝑂𝑈𝑇 𝑠𝑡𝑎𝑑𝑦 𝑠𝑡𝑎𝑡 𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

The Strategy for Solving Problems:-

1. Read and understand the problem statement.

.)‫اقرأ وافهم السؤال جيدا(المشكلة‬.1
2. Draw a sketch of the process and specify the system boundary.
ً ‫ارسم مخط‬.2
.‫طا للعملية وحدد حدود النظام‬
3. Place labels (symbols, numbers, and units) on the diagram for all of the
known flows, materials, and compositions. For the unknown flows,
materials, and compositions insert symbols and units. Add any other
useful relations or information.
.‫ضع ملصقات (الرموز واألرقام والوحدات) على الرسم البياني لجميع التيارات والمواد والتركيبات المعروفة‬.3
.‫ أدخل الرموز والوحدات أضف أي عالقات أو معلومات مفيدة أخرى‬، ‫بالنسبة للتيارات والمواد والتركيبات غير المعروفة‬
4. Obtain any data you need to solve the problem, but are missing.
.‫ وهي مفقودة‬، ‫ الحصول على أي بيانات تحتاجها لحل المشكلة‬.4
5. Choose a basis.
.‫ اختر األساس‬.5
6. Determine the number of variables whose values are unknown (the
unknowns).
.)‫ تحديد عدد المتغيرات التي تكون قيمها غير معروفة (المجهولة‬. 6
7. Determine the number of independent equations and carry out a degrees
of freedom analysis.
.‫ تحديد عدد المعادالت المستقلة وإجراء درجات الحرية لغرض التحليل‬. 7

3
‫‪Principles ch.8‬‬ ‫‪Dr. Hameed R. Alamery‬‬

‫موازنة مادة بدون تفاعل كيمياوي وعلى جهاز واحد‬

‫الكمية الداخلة لكل مادة = كميتها الخارجة‬

‫‪IN = OUT‬‬

‫كمية بالوزن للمادة‬

‫𝑡𝑤‬
‫نسبة مئوية الوزنية‬ ‫= ‪𝑤𝑡 %‬‬
‫𝑡𝑤 𝑙𝑎𝑡𝑜𝑇‬
‫‪× 100‬‬

‫الوزن الكلي للخليط او المحلول (‪ )basis‬قيمة خط‬

‫في حالة عدم أعطاء ‪( basis‬ال وزن والحجم وال موالت الخليط) يتم فرض‬
‫‪ Basis‬من قبل الطالب‪.‬‬
‫‪ ‬يمكن عمل موازنات بقدر عدد المواد الموجدة بالجهاز باالضافة الى‬
‫‪ T.M.B‬تعني (‪)TOTAL MATERIAL BALANCE‬‬ ‫معادلة‬
‫يستفاد منها للتحقق من صحة الحل ‪Checking‬‬

‫‪4‬‬
Principles ch.8 Dr. Hameed R. Alamery

Equipment:-
1// divider:-
F
A =10%
B=90%
Divider

P2 P1
A =10% A=10%
B=90% B =90%
M.B. on A
(10/100 )*F = (10/100)*P1 + (10/100)*P2
F = P1 + P2

M.B. on B
(90/100)*F=(90/100)*P1 + (90/100)*P2

T.M.B.
F= P1+ P2

5
 Principles ch.8 Dr. Hameed R. Alamery

2// DISTILLATION:-
Distillat (D)
A%
B%
Feed (F)
A%
B% West (W)
A%
B%

3// Absorption
(G) (L)

Abso.
Colum

Feed (F) (P)

6
Principles ch.8 Dr. Hameed R. Alamery

4// FILTER:-
S
A%
B%

FILTER

Cake A% filtrate A%
Ppt. B% B%

5// Extraction unit

S (solvent)

F (feed) Extraction unit R (residue)

A% A%
B% B%
P (product)
Solvent %
A%

7
 Principles ch.8 Dr. Hameed R. Alamery

Material balances without chemical reactions.

EXAMPLE 8.2-: Separation of Gases Using a Membrane:
Membranes represent a relatively new technology for the separation of gases. One use that
has attracted attention is the separation of nitrogen and oxygen from air. Figure E8.2a
illustrates a nano porous membrane that is made by coating a very thin layer of polymer on
a porous graphite supporting layer. What is the composition of the waste stream if the waste
stream amounts to 80% of the input stream?

Solution:-

Step 1
This is an open, steady-stat process without chemical reaction. The system is the membrane
as depicted in Figure E8.2. Let yo 2 be the mole fraction of oxygen as depicted in Figure
E8.2) yN2 be the mole fraction of nitrogen, and let no 2 and nN2 be the respective moles.

Steps 2, 3, and 4
All of the data and symbols have been placed, in Figure E8.2b.
Step5

8
 Principles ch.8 Dr. Hameed R. Alamery

Pick a convenient basis.

Basis: 100 g mol. = F
A degree of freedom analysis that includes all of the variables comes next.
You could either use moles or mole fractions as the unknowns.

Steps 6 and 7

Number of variables: 9
F, P, Wand 6 ni
Number of equations: 9

Basis: F= 100

9
Principles ch.8 Dr. Hameed R. Alamery

10
 Principles ch.8 Dr. Hameed R. Alamery

Material balances
Example 1:-
It is required to prepare 1250 kg of a solution composed of 12 wt. % ethanol and 88 wt. %
water. Two solutions are available, the first contains 5 wt. % ethanol, and the second
contains 25 wt. % ethanol. How much of each solution are mixed to prepare the desired
solution?
25 % Ethanol
Solution: 5 % Ethanol 75 % water
95 % water B
Basis: 1250 kg of M A

1. Ethanol balance

5 25 12 12 % Ethanol
A( )+𝐵( ) = 𝑀( )
100 100 100 88 % water
M =1250 kg
𝟎. 𝟎𝟓 𝐀 + 𝟎. 𝟐𝟓 𝑩 = 𝟎. 𝟏𝟐(𝟏𝟐𝟓𝟎) = 𝟏𝟓𝟎

150 − 0.25 𝐵
A= = 3000 − 5 𝐵 … … … . (1)
0.05

2. Water balance

0.95 A + 0.75 𝐵 = 0.88 M = 0.88(1250) = 1100 … … … … … . . (2)

Sub. Eq. (1) in eq. (2)

0.95 (3000 − 5 𝐵) + 0.75 𝐵 = 1100
2850 − 4.75 B + 0.75 𝐵 = 1100
4 𝐵 = 1750 → 𝑩 = 𝟒𝟑𝟕. 𝟓 𝒌𝒈
Sub. in eq. (1) A = 3000 − 5(437.5) = 812.5 kg

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐴 + 𝐵 = 437.5 + 812.5 = 1250 𝑘𝑔/ℎ𝑟

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑀 = 1250 𝑘𝑔/ℎ𝑟

1
 Principles ch.8 Dr. Hameed R. Alamery

Example 2:-
A binary mixture consists of 35% benzene and 65% toluene are continuously fed to the
distillation column at rate of 1000 Ib mole/hr. The distillate (top product) contains 85 mol.
% benzene, whereas the residue (bottom product) contains 95 mol. % toluene. Calculate
the quantities of distillate and residue obtained per hour.
Solution:
35 mole % benzene D
65 mole % toluene 85% benzene
F= 1000 Ib mole/hr 15 % toluene
Distillation

Column

5 mol. % benzene
Basis: 1 hr. ≡ 1000 Ib mole of F 95 mol. % toluene
W
1. Total material balances
𝐹 = 𝐷 + 𝑊 → 𝟏𝟎𝟎𝟎 = 𝑫 + 𝑾 … … … … … … … . (1)
2. Material balance on the benzene
𝑭 𝑿𝑭 = 𝑫𝑿𝑫 + 𝑾𝑿𝑾
𝑊ℎ𝑒𝑟𝑒 𝑋𝐹 , 𝑋𝐷 , 𝑎𝑛𝑑 𝑋𝑊 are the mole fraction of benzene in the feed, distillate and
bottom product respectively.
35 85 5
1000 ( )=𝐷 ( )+𝑊( )
100 100 100

350 = 0.85 𝐷 + 0.05 𝑊 … … … … … … … (2)

Sub. Eq. (1) in eq. (2)
350 = 0.85 𝐷 + 0.05 (1000 − D)
300
350 = 0.85 𝐷 + 50 − 0.05 D → 300 = 0.8D → D = = 375 Ib mole/hr
0.8
Sub. In eq. (1)
𝑊 = 1000 − 375 = 625 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟
𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝒕𝒐𝒍𝒖𝒆𝒏𝒆 𝒃𝒂𝒍𝒂𝒏𝒄𝒆
65
Toluene input = 𝐹 ( ) = 650 𝐼𝑏𝑚𝑜𝑙𝑒
100
15 95
Toluene output = 𝐷 ( )+𝑊( ) = 375(0.15) + 625(0.95)
100 100
= 56.25 + 593.75 = 650 𝐼𝑏 𝑚𝑜𝑙𝑒

2
 Principles ch.8 Dr. Hameed R. Alamery

Example 3:-
100 kg of nitric acid solution (N) containing 40 wt. % HNO3 and 60 wt. % water are mixed
with sulfuric acid solution (S). 25% of total water input are evaporated (V). The final
mixture (M) contains 16 wt. % HNO3, 24wt. % H2SO4 and 60 wt. % water. Calculate:-
A// the quantities of the final mixture (M) and water vapor (V).
B// the mass and composition (wt. %) of sulfuric acid solution(S).
Solution:
V

S
N = 100 kg H2SO4
40 % HNO3 water
60 % water

Basis: 100 kg of N
M
1. HNO3 balance (Tie component). 16 % HNO3
60 % water
24 % H2SO4
40 16 𝟒𝟎
N( ) = 𝑀( ) → 100(0.4) = 0.16 𝑀 → 𝑴 = = 𝟐𝟓𝟎 𝒌𝒈
100 100 𝟎. 𝟏𝟔

2. H2SO4 balance.
Let x= wt. fraction of H2SO4 in (S), hence (1-x) = wt. fraction of water
24
𝑆𝑋 = 𝑀( ) = 250(0.24) = 𝟔𝟎 → 𝑆𝑋 = 60 … … … … … … (1)
100

3. Water balance.

60
Water input = N ( ) + 𝑆 (1 − 𝑥 ) = 60 + 𝑆 − 𝑆𝑋
100

75
Water output in M = ( ) 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑖𝑛𝑝𝑢𝑡
100

∴ 250 (0.6) = 0.75 (60 + 𝑆 − 𝑆𝑋) … … … … … … … . . (2)

Sub. Eq. (1) in eq. (2)

3
 Principles ch.8 Dr. Hameed R. Alamery

150 60
150 = 0.75 (60 + 𝑆 − 60) = 0.75 𝑆 →𝑆= = 200 𝑘𝑔 & 𝑋= = 0.3
0.75 200

𝑆 𝐶𝑜𝑛𝑠𝑖𝑠𝑡𝑠 𝑜𝑓 30 % 𝐻2𝑆𝑂4 𝑎𝑛𝑑 70 % 𝑊𝑎𝑡𝑒𝑟

25
Water Vapour (V) = of water input
100

= 0.25 [60 + S (1 − x)] = 0.25 [60 + 200 (0.7)] = 50 𝑘𝑔

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝑁 + 𝑆 = 100 + 200 = 300 𝑘𝑔

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑀 + 𝑉 = 250 + 50 = 300 𝑘𝑔

4
 Principles ch.8 Dr. Hameed R. Alamery

Example 4:-
A gaseous mixture (F) consists of 16 mol. % CS2 and 84 mol. % air are continuously fed
to the absorption column at a rate of 1000 Ib mole /hr. Most of CS 2 input are absorbed by
liquid benzene (L) which fed to the top of the column. 1 % of benzene input are evaporated
and out with the exit gas stream (G) which consists of 96 mol. % air, 2 mol. % CS 2 and
2mol. % benzene. The product liquid stream (P) consists of benzene and CS2. Calculate
the molal flow rates of (G), (L), (P) and the composition of (P).
Solution:

G L
96 % Air Benzene
2 % CS2
2 % benzene Absorption

Column

F= 1000 Ib mole/hr CS2

16 % CS2 Benzene
84 % Air P

Basis: 1 hr. ≡ 1000 Ib mole of F

1. Air balances (Tie component).

84 96 840
F( )=𝐺( ) → 840 = 0.96𝐺 → 𝐺=( ) = 875 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟
100 100 0.96

2. Benzene balances.
2
benzene in G = 875 ( ) = 17.5 𝐼𝑏 𝑚𝑜𝑙𝑒
100
1
17.5 = 1% of benzene input = 100 (𝐿) → ∴ 𝐿 = 17.5(100) = 1750 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟

99
benzene in P = 99 % of benzene input = (𝐿) = 0.99 (1750) = 1732.5 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟
100
Let x= mole fraction of benzene in (P)
𝑃 𝑋 = 1732.5 … … … … … … (1)

5
 Principles ch.8 Dr. Hameed R. Alamery

3. CS2 balances.

16 2
F( ) = G( ) + 𝑃 (1 − 𝑥 )
100 100

1000 (0.16) = 875(0.02) + 𝑃 − 𝑃𝑋 → 160 = 17.5 + 𝑃 − 1732.5 →

𝑃 = 1875 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟

1732.5
Sub. in (1) ∴𝑋= = 0.924 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑏𝑒𝑛𝑧𝑒𝑛 𝑖𝑛 (𝑃)
1875

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐹 + 𝐿 = 1000 + 1750 = 2750 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐺 + 𝑝 = 875 + 1875 = 2750 𝐼𝑏 𝑚𝑜𝑙𝑒/ℎ𝑟

6
 Principles ch.8 Dr. Hameed R. Alamery

Example 5:-
A waxed paper (F) containing 25 wt. % wax and 75 wt. % paper pulp are continuously fed
at a rate of 1000 Ib/hr to a certain extraction unit in which 98% of the wax input to the unit
to the unit are extracted by 37 °API kerosene (S). The extracted paper out from the extractor
(R) contains 40 wt. % paper pulp, the reminder being kerosene and un-extracted wax. The
product solution (P) consists of 80 % kerosene & 20 wt. % wax. Calculate:-
a// The flow rates of S, R and P. b// The composition of R.
c// Gallons of kerosene input to the unit per hour.
Solution:

F= 1000 Ib /hr S
25 % Wax Kerosene
Extraction
75 % Pulp
Unit

P
80 % Kerosene
R 20 % Wax
60 % Kerosene +Wax
Basis: 1 hr. ≡ 1000 Ib of F 40 % Pulp
a. Pulp balance (Tie component).

75 40 750
F( ) = 𝑅( ) → 750 = 0.4𝑅 → 𝑅 = ( ) = 1875 𝐼𝑏/ℎ𝑟
100 100 0.4

b. Wax balance
25
Wax input = 1000 ( ) = 250 𝐼𝑏
100
98 20 245
Wax in (P) = 250 ( ) = 245 = 𝑃 ( ) →𝑃= = 1225 𝐼𝑏/ℎ𝑟
100 100 0.2
2
Wax in (R) = 250 ( ) = 5 𝐼𝑏
100

c. Kerosene balance

60
(Kerosene + Wax)in R = 1875 ( ) = 1125 𝐼𝑏
100

(Kerosene) in R = 1125 − 5 = 1120 𝐼𝑏

7
 Principles ch.8 Dr. Hameed R. Alamery

1120
Composition of R: (Kerosene) = ( ) × 100 = 59.73 %;
1875
5
𝑊𝑎𝑥 = × 100 = 0.27 %
1875
80
𝑆 = 1120 + 𝑃 ( ) → 𝑆 = 1120 + 1225(0.8) = 2100 𝐼𝑏/ℎ𝑟
100

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐹 + 𝑆 = 1000 + 2100 = 3100 𝐼𝑏/ℎ𝑟

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑅 + 𝑃 = 1875 + 1225 = 3100 𝐼𝑏/ℎ𝑟

8
‫‪Principles ch.9‬‬ ‫‪Dr. Hameed R. Alamery‬‬

‫‪Material balance without chemical reaction on multi process.‬‬

‫‪IN =OUT‬‬

‫*اما يتم تقسيم كل جهاز على حدى أو تأخذ جميع األجهزة كجهاز واحد فتسمى عملية‬
‫الموازنة في هذه الحالة ‪overall M. B.‬‬
‫‪%D‬‬ ‫‪%A‬‬
‫‪%B‬‬ ‫‪%C‬‬

‫‪%A‬‬
‫‪%B‬‬ ‫‪1‬‬ ‫‪2‬‬ ‫‪3‬‬

‫‪%D‬‬
‫‪%C‬‬ ‫‪%B‬‬

‫عند عمل الموا زنة من نوع ‪ overall‬يتم اهمال الخطوط البينية‬

‫‪ .1‬اذا كانت الخطوط البينية معلومة (كمية خط ) او نسب الموا د في ذلك الخط ‪ .‬يتم تقسيم كل‬
‫جهاز على حدى‪.‬‬
‫‪ .2‬اما اذا كانت الخطوط البينية مجهولة فنعمل موازنة من نوع ‪ overall M.B.‬دمج لالجهزة‪.‬‬

‫‪1‬‬
 Principles ch.9 Dr. Hameed R. Alamery

Example 6:-
Acetone can be recovered from a gaseous mixture by absorption followed by distillation.
The feed gas (F) consists of 94 wt. % air, 5 wt. % acetone and 1 wt. % humidity (water)
are continuously fed to the absorption column at rate of 1000 kg/hr. Water stream (S) enters
the top of the column. The exit gases (G) consists of 97 wt. % air and 3 wt. % water. The
exit liquid stream (L) enters the distillation column with composition of 20 wt. % acetone
&80 wt. % water. The top product (D) consists of 98 wt. % acetone, whereas the bottom
product (W) consists 99.5 wt. % water. Calculate the flow rates of S, G, L, D and W.

Solution:- S
Water D
G 98% Acetone
97 % Air 2% water
3 % water
Absorption Distillation

Column Column

F =1000 kg/hr
94% Air
5 % Acetone
1 % water W
L 0.5% Acetone
20 % Acetone 99.5% water
80 % water

Basis: 1 hr. ≡ 1000 kg of F

1. Material balances on Absorption Column

a. Air balances (Tie component).

94 97 940
F( )=𝐺( ) → 940 = 0.97𝐺 → 𝐺 = ( ) = 969 𝑘𝑔/ℎ𝑟
100 100 0.97

b. Acetone balances (Tie component).

5 20 50
F( ) = 𝐿( ) → 50 = 0.2 𝐿 → 𝐿 = ( ) = 250 𝑘𝑔/ℎ𝑟
100 100 0.2

c. Water balances.
1 80 3
F( )+𝑆 = 𝐿( )+𝐺( )
100 100 100

2
 Principles ch.9 Dr. Hameed R. Alamery

10 + 𝑆 = 250 (0.8) + 969 (0.03) → 𝑆 = 200 + 29 − 10 = 219 𝑘𝑔/ℎ𝑟

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐹 + 𝑆 = 1000 + 219 = 1219 𝑘𝑔/ℎ𝑟

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐺 + 𝐿 = 969 + 250 = 1219 𝑘𝑔/ℎ𝑟

2. Material balances on Distillation Column

a. 𝑻𝒐𝒕𝒆𝒍 Material balances 𝑳 = 𝑫 + 𝑾 → 250 = 𝐷 + 𝑊

20 98 0.5
b. Acetone balances L (100) = 𝐷 (100) + 𝑊 (100) → 𝐷 = 50 𝑘𝑔/ℎ𝑟

𝑤 = 200 𝑘𝑔/ℎ𝑟

𝟑. 𝑭𝒊𝒏𝒂𝒍 𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩. 𝒐𝒗𝒆𝒓𝒂𝒍𝒍 𝒕𝒉𝒆 𝒑𝒓𝒐𝒄𝒆𝒔𝒔

𝐼𝑛𝑝𝑢𝑡 = 𝐹 + 𝑆 = 1000 + 219 = 1219 𝑘𝑔/ℎ𝑟

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐺 + 𝐷 + 𝑊 = 969 + 50 + 200 = 1219 𝑘𝑔/ℎ𝑟

3
 Principles ch.9 Dr. Hameed R. Alamery

Example 7:-
A slurry (S) containing 40 wt. % CaCO3 and 60 wt. % water are continuously fed at a rate
of 1000 kg/hr to the filtration unit in which only 1 % of fine particles of CaCO3 are passed
through the filter cloth and out with the filtrate (F). The wet cake (C) are discharged in a
continuous manner and input to the drying unit in which hot dry air (A) are passed over it,
producing a product (P) consists of 99 wt. % CaCO3 and 1 wt. % water. The exit air (G)
contains 0.05 kg water/ 1kg dry air. The mass ratio between C and P = 1.1/1. Calculate the
flow rates of F, C, A, P and the composition of the wet cake(C) and the filtrate (F).

G
0.05 kg water
1kg dry air

C
Filtration unit Drying unit P
99 % CaCO3
S 1 % water
40 % CaCO3
60 % water
F
A 100 % Air

Solution:-
Basis: 1 hr. ≡ 1000 kg of S
1- Material balances on the CaCO3

40
CaCO3 input = S () = 1000 (0.4) = 400 𝑘𝑔
100
1
CaCO3 out with F = 400 ( ) = 4 𝑘𝑔
100
99 396
CaCO3 in P = 400 − 4 = 396 = P ( )→𝑃= = 400 𝑘𝑔
100 0.99
C 1.1
= → C = 1.1 (P) = 1.1 (400) = 440 𝑘𝑔/ℎ𝑟
𝑃 1
2- Material balances on Filtration unit
T. M. B. S = C + F → F = S − C = 1000 − 440 = 560 𝑘𝑔/ℎ𝑟
water in F = F − CaCO3 in F = 560 − 4 = 556 𝑘𝑔
4 556
Composition of F ∶ Caco3 = ( ) × 100 = 0.7% , 𝑤𝑎𝑡𝑒𝑟 = ( ) × 100 = 99.3%
560 560

4
 Principles ch.9 Dr. Hameed R. Alamery

CaCO3 in C = CaCO3 in S − CaCO3 in F = 400 − 4 = 396 𝑘𝑔

water in C = C − CaCO3 in c = 440 − 396 = 44 𝑘𝑔

396 44
Composition of C: Caco3 = ( ) × 100 = 90% , 𝑤𝑎𝑡𝑒𝑟 = ( ) × 100 = 10%
440 440

3- Material balances on Drying unit

1
𝑤𝑎𝑡𝑒𝑟 𝑜𝑢𝑡 𝑤𝑖𝑡ℎ 𝑎𝑖𝑟 = water in C − water in P = 44 − 400( ) = 40 𝑘𝑔
100
1 𝑘𝑔 𝑎𝑖𝑟 𝑘𝑔
𝐴 = 40 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 (0.05 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 ) = 800 ℎ𝑟 ,,, G = A+40 = 840 kg/hr

H2O AIR
0.05 1 KG
40 X

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩. 𝒐𝒗𝒆𝒓𝒂𝒍𝒍 𝒕𝒉𝒆 𝒑𝒓𝒐𝒄𝒆𝒔𝒔

𝐼𝑛𝑝𝑢𝑡 = 𝑆 + 𝐴 = 1000 + 800 = 1800 𝑘𝑔/ℎ𝑟

𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐹 + 𝑃 + 𝐺 = 560 + 400 + 840 = 1800 𝑘𝑔/ℎ𝑟

5
 Principles ch.9 Dr. Hameed R. Alamery

Example 8:-
The manufacture of sugar con to represent by the following block diagram:

Water V
13 % Sugar
73 % water
15 % Sugar
14 % Pulp 85 % water
Mill Filter Evaporator

E H
F
16 % Sugar B S
25 % water
59 % Pulp B Bagasse Solid K
80 % Pulp 95 % Pulp 40 % Sugar
5 % (water + sugar)
20 % water + sugar 60 % water

L Water Crystallizer

Sugar P
Make material balance calculations to calculate the 1000 Ib/hr
Flow rates and composition of all streams in the process.

Solution:
Basis: 1000 Ib of F
1- Material balances on the Mill
a. Pulp balance
F (0.59) = 𝐸 (0.14) + 𝐵 (0.86) → 590 = 0.14𝐸 + 0.8 𝐵 … … … … (1)

b. (Sugar +water) balance

F (0.41) = 𝐸 (0.86) + 𝐵 (0.2) → 410 = 0.86 𝐸 + 0.2 𝐵 … … … … (2)

Sub. Eq. (1) in (2)

6
Principles ch.9 Dr. Hameed R. Alamery

590 − 0.14 𝐸
410 = 0.2 ( ) + 0.86 𝐸 → 𝟒𝟏𝟎 = 𝟏𝟒𝟕. 𝟓 − 𝟎. 𝟎𝟑𝟓 𝑬 + 𝟎. 𝟖𝟔 𝑬
0.8
262.5
𝟎. 𝟖𝟐𝟓 𝑬 = 𝟐𝟔𝟐. 𝟓 → 𝐸=( ) = 318.2 Ib
0.825
Sub. In Eq. (1)
590 − 0.14 𝐸 590 − 0.14 (318.2)
𝐵=( ) = ( ) = 𝟔𝟖𝟏. 𝟖 𝑰𝒃
0.8 0.8

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐹 = 1000
𝑂𝑢𝑡𝑝𝑢𝑡 = 𝐸 + 𝐵 = 318.2 + 681.8 = 1000 𝐼𝑏
c. Sugar balance

F (0.16) = 𝐸 (0.13) + 𝐵 X 𝑋 ∶ 𝑤𝑡. 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑢𝑔𝑎𝑟 𝑖𝑛 𝐵

160 = 318.2 (0.13) + 681.8 X → 𝑋 = 0.174 , 𝑆𝑢𝑔𝑎𝑟 𝑖𝑛 𝐵 = 17.4 𝑤𝑡. %

d. Water balance

F (0.25) = 𝐸 (0.73) + 𝐵 y 𝑦 ∶ 𝑤𝑡. 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑖𝑛 𝐵

250 = 318.2 (0.73) + 681.8 y → 𝑦 = 0.026 , 𝑊𝑎𝑡𝑒𝑟 𝑖𝑛 𝐵 = 2.6 𝑤𝑡. %
𝐶ℎ𝑒𝑐𝑘𝑖𝑛𝑔 (𝑋 + 𝑦) = 0.174 + 0.026 = 0.20
2- Material balances on the Filter
a. Pulp balance
E (0.14) = 𝑆 (0.95) → 318.2 (0.14) = (0.95)𝑆 → 𝑆 = 46.9 𝐼𝑏
b. (Sugar +water) balance
100
E (0.86) = 𝑆 (0.05) + 𝐻 ( ) → ∴ 𝐻 = 318.2 (0.86) − 46.9(0.05)
100
→ 𝐻 = 273.6 2.3 = 271.3

7
Principles ch.9 Dr. Hameed R. Alamery

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐸 = 318.2
𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑆 + 𝐻 = 46.9 + 271.3 = 318.2
c. Sugar balance

E (0.13) = 𝐻 (0.15) + 𝑆 X 𝑋 ∶ 𝑤𝑡. 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑢𝑔𝑎𝑟

318.2 (0.13) = 271.3 (0.15) + 46.9 𝑋 → 41.37 = 40.7 + 46.9𝑋
→ 𝑋 = 0.014 , 𝑆𝑢𝑔𝑎𝑟 𝑖𝑛 𝑆 = 1.4 𝑤𝑡. %
d. Water balance

𝐸 (0.73) = 𝑆 y + 𝐻(0.85) 𝑦 ∶ 𝑤𝑡. 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

318.2 (0.73) = 46.9 𝑦 + 271.3(0.85) → 232.3 = 46.9𝑦 + 230.6
𝑦 = 0.036, 𝑤𝑎𝑡𝑒𝑟 𝑖𝑛 𝑆 = 3.6 𝑤𝑡. %
𝐶ℎ𝑒𝑐𝑘𝑖𝑛𝑔 (𝑋 + 𝑦) = 0.014 + 0.036 = 0.05

3- Material balances on the Evaporator

a. Sugar balance
271.3 (0.15)
𝐻 (0.15) = 𝐾 (0.4) 𝐾= = 101.4 𝐼𝑏
0.4

b. Water balance

𝐻 (0.85) = 𝑉 + (0.6) 𝐾 → 𝑉 = 271.3(0.85) − 0.6 (101.7) =

→ 𝑉 = 230.6 − 61 = 169.6 𝐼𝑏

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.

𝐼𝑛𝑝𝑢𝑡 = 𝐻 = 271.6 𝐼𝑏
𝑂𝑢𝑡𝑝𝑢𝑡 = 𝑉 + 𝐾 = 169.6 + 101.7 = 271.6 𝐼𝑏

8
Principles ch.9 Dr. Hameed R. Alamery

4- Material balances on the Crystallizer

a. Water balance
(0.6) 𝐾 = 𝐿 → 𝐿 = 101.7 (0.6) = 61 𝐼𝑏

b. Sugar balance
(0.4) 𝐾 = 𝑃 → 𝑃 = 101.7 (0.4) = 40.7 𝐼𝑏
𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈 𝑻. 𝑴. 𝑩.
𝐿 + 𝑃 = 61 + 40.7 = 101.7 𝐼𝑏

𝑭𝒊𝒏𝒂𝒍 𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈

Overall Material balance

𝑇𝑜𝑡𝑎𝑙 𝑖𝑛𝑝𝑢𝑡 = 𝐹 = 1000 𝐼𝑏
𝑇𝑜𝑡𝑎𝑙 𝑜𝑢𝑡𝑝𝑢𝑡 = 𝐵 + 𝑆 + 𝑉 + 𝐿 + 𝑃
= 681.8 + 46.9 + 169.6 + 61 + 40.7 = 1000 𝐼𝑏

Change the basis to 1000 Ib of P

F B E S H V K L P
1000 681.8 318.2 46.9 271.3 169.6 101.7 61 40.7
24.570 16752 7818 1152 6666 4167 2499 1499 1000

9
‫‪Principles ch.10‬‬ ‫‪Dr. Hameed R. Alamery‬‬

‫‪Material balances with chemical reactions.‬‬

‫‪Material balance with reaction:-‬‬

‫𝐷‪𝐴+𝐵 →𝐶+‬‬ ‫‪ ‬موازنة مادة تفاعل كيمياوي‬

‫‪ ‬هذه هي موازنة كل مادة قبل السهم في المعادلة الكيمياوية‬

‫)𝑡𝑢𝑜 ‪(𝐼𝑛 = 𝑟𝑒𝑎𝑐𝑡 +‬‬

‫‪ ‬هذه هي موازنة كل مادة بعد السهم في المعادلة الكيمياوية‪.‬‬

‫𝑡𝑢𝑜 = 𝑡𝑐𝑢𝑑𝑜𝑟𝑝 ‪𝐼𝑛 +‬‬

‫‪ ‬هذه هي موازنة كل مادة البعد السهم والقبل السهم في المعادلة مثل‬

‫)عامل مساعد‪(Ash, impurities ,‬‬
‫𝑡𝑢𝑜 = 𝑛𝐼‬

‫‪ ‬أليجاد ‪react:‬‬
‫‪ .1‬تعطى كمية مادة بعد السهم لغرض عمل المقارنة‪.‬‬
‫𝑡𝑐𝑎𝑒𝑟‬
‫= ‪𝑐𝑜𝑛𝑣.‬‬ ‫‪ .2‬او تعطى‬
‫𝑛𝑖‬
‫𝑡𝑐𝑎𝑒𝑟‬
‫= 𝑛𝑜𝑖𝑡𝑒𝑙𝑝𝑚𝑜𝑐 𝑓𝑜 𝑒𝑒𝑟𝑔𝑑‬ ‫‪ .3‬او تعطى‬
‫𝑛𝑖‬

‫‪ The reaction goes to completion‬‬

‫‪ The reaction is completely conversion‬‬
‫‪In = react‬‬

‫‪1‬‬
‫‪Principles ch.10‬‬ ‫‪Dr. Hameed R. Alamery‬‬

‫‪ ‬طريقة الحل‪:‬‬
‫‪ ‬يجب ايجاد ‪ react‬حسب الطرق السابقة‬
‫‪ ‬يتم عمل موازنات بقدر عدد المواد الموجودة بالجهاز مع االخذ االعتبار(موقع المادة)‬

‫في المعادلة الكيمياوية‪.‬‬

‫‪ ‬الحل يكون با لموالت ولكن‬

‫‪Checking‬‬
‫)𝑡𝑢𝑜( 𝑠𝑠𝑎𝑚 𝑙𝑙𝑎𝑡𝑜𝑇 = )𝑛𝐼( 𝑠𝑠𝑎𝑚 𝑙𝑙𝑎𝑡𝑜𝑇‬

‫‪ ‬الحل يكون اغلب االحيان ‪ overall M.B.‬الن الخطوط البينية غالبا ماتكون مجهولة‪.‬‬

‫‪React‬‬ ‫‪IN‬‬
‫‪Produced‬‬ ‫‪OUT‬‬

‫من المقارنة‬ ‫من رسم الجهاز‬

‫‪2‬‬
 Principles ch.10 Dr. Hameed R. Alamery

Example 1:-
A gaseous mixture consists of 80 mol. % N2 and 20 mol. % CO2 are
continuously fed to the absorption column in which CO2 are completely
absorbed by sodium hydroxide solution according to the following reaction:
𝐶𝑂2 + 2𝑁𝑎𝑂𝐻 → 𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂
M wt. 44 40 106 18
The product liquid stream are left the bottom of the absorber at a rate of 1000
Ib/hr with composition of 26.5 wt. % Na2CO3, 4 wt. % NaOH and 69.5 wt. %
H2O. Pure nitrogen are out from the top of the column. Calculate:
a. The mass flow rate and composition (wt. %) of NaOH solution.
b. The mass flow rates of input & output gaseous stream.
c. % excess and conversion of NaOH.
Solution:
Basis: 1 hr. ≡ 1000 Ib. of product solution
a.
26.5 265
𝑁𝑎2 𝐶𝑂3 produced = 1000( ) = 265 𝐼𝑏 → = 2.5 𝐼𝑏 𝑚𝑜𝑙
100 106
2
NaOH reacted = 2.5 ( ) = 5 𝐼𝑏 𝑚𝑜𝑙𝑒 = 5 × 40 = 200 𝐼𝑏 NaOH Na2CO3
1 2 1
4
NaOH output = 1000 ( ) = 40 𝐼𝑏 X 2.5
100

∴ NaOH input = 200 + 40 = 240 𝐼𝑏

𝑆𝑖𝑚𝑖𝑙𝑎𝑟𝑙𝑦 𝐻2 O produced from reaction = 2.5 Ib mole = 2.5(18) = 45 Ib

69.5
𝐻2 O output = 1000 ( ) = 695 𝐼𝑏 H2O Na2CO3
100
1 1
∴ 𝐻2 O input = 695 − 45 = 650 𝐼𝑏
∴ NaOH solution input = 240 + 650 = 890 𝐼𝑏/ℎ𝑟 X 2.5

Na OH = (240/ 890) X 100 = 27 %

H2O = (650/890) X 100 = 73 %

3
Principles ch.10 Dr. Hameed R. Alamery

b.
26.5 265
𝑁𝑎2 𝐶𝑂3 produced = 1000( ) = 265 𝐼𝑏 → = 2.5 𝐼𝑏 𝑚𝑜𝑙
100 106
𝐶𝑂2 reacted = 2.5 𝐼𝑏 𝑚𝑜𝑙𝑒 = 𝐶𝑂2 𝑖𝑛𝑝𝑢𝑡
(𝑠𝑖𝑛𝑐𝑒 𝐶𝑂2 𝑎𝑟𝑒 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑙𝑦 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
80
𝑁2 input = 2.5 ( ) = 10 𝐼𝑏 𝑚𝑜𝑙𝑒
20
∴ flow rate of feed gas = 2.5 (44) + 10 (28) = 390 𝐼𝑏 /ℎ𝑟

flow rate of exit gas = 10 (28) = 280 𝐼𝑏⁄ℎ𝑟

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈:
𝑰𝒏𝒑𝒖𝒕 = 𝟖𝟗𝟎 + 𝟑𝟗𝟎 = 𝟏𝟐𝟖𝟎 𝑰𝒃/𝒉𝒓
𝑶𝒖𝒕𝒑𝒖𝒕 = 𝟏𝟎𝟎𝟎 + 𝟐𝟖𝟎 = 𝟏𝟐𝟖𝟎 𝑰𝒃/𝒉𝒓

c.
CO2 Na2CO3
1
𝐶𝑂2 input = quantity reacted = 2.5 ( ) = 2.5 𝐼𝑏 𝑚𝑜𝑙𝑒 1 1
1
X 2.5

240
NaOH input = 240 𝐼𝑏 = = 6 𝐼𝑏 𝑚𝑜𝑙𝑒
40

CO2 NaOH
𝑖𝑛𝑝𝑢𝑡 − 𝑡ℎ𝑒𝑜. 6−5
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻 = × 100 = × 100 = 20 % 1 2
𝑡ℎ𝑒𝑜. 5
2.5 X

𝑁𝑎𝑂𝐻 𝑟𝑒𝑐𝑡𝑒𝑑 5
% 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑂𝐹 𝑁𝑎𝑂𝐻 = × 100 = × 100 = 83.3 %
𝑁𝑎𝑂𝐻 𝑖𝑛𝑝𝑢𝑡 6
(𝐷𝐸𝑃𝐸𝑁𝐷 𝑂𝑁 𝑇𝐻𝐸 𝐸𝑋𝐶𝐸𝑆𝑆 )

4
 Principles ch.10 Dr. Hameed R. Alamery

Example 2:-
Hydrofluoric acid can be manufactured by treading crushed flow with an
excess amount of sulfuric acid solution according to the:
𝐶𝑎𝐹2 + 𝐻2 𝑆𝑂4 → 𝐶𝑎𝑆𝑂4 + 2𝐻𝐹
M wt. 78 98 136 20
The fluorspar ore (F) contains 78 wt. % CaF2 & 22 wt. % inert
impurities. The acid solution (S) contain 95 wt. % H2SO4. The reaction goes
to completion and all HF and water are volatilized and separated as vapour
(V) from residual sulfate cake (R) which contains 16 wt.% H2SO4. On the
basis of 1000 Ib of the fluorspar charged.
Calculate (a) the quantities of S, V, R and the composition of (v) & (R).
(b) % excess of H2SO4.
Solution:
Basis: 1000 Ib. of F
78 780
a. Ca𝐹2 input = 1000 ( ) = 780 𝐼𝑏 = = 10 𝐼𝑏 𝑚𝑜𝑙𝑒 =
100 78
𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑠𝑖𝑛𝑐𝑒 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑔𝑜𝑒𝑠 𝑡𝑜 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑖𝑜𝑛

𝐼𝑚𝑝𝑢𝑟𝑖𝑡𝑖𝑒𝑠 𝑖𝑛𝑝𝑢𝑡 = 220 𝐼𝑏 = 𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑜𝑢𝑡𝑝𝑢𝑡 𝑖𝑛 (𝑅)

Ca𝑆𝑂4 produced = 10 (136) = 1360 𝐼𝑏
84
∴ Ca𝑆𝑂4 + 𝐼𝑚𝑝𝑢𝑟𝑖𝑡𝑖𝑒𝑠 = 1360 + 220 = 1580 𝐼𝑏 = 𝑅( )
100

1580 × 100
∴R= ( ) = 1881 𝐼𝑏 Composition of (R).
84
16 Ca SO4 = (1360 / 1881) X 100 =72.3 %
∴ 𝐻2𝑆𝑂4 in R = 1881 ( ) = 301 𝐼𝑏
100 Impurities = (220/1881) X 100= 11.7%
H2SO4 = 16 %

∴ 𝐻2 𝑆𝑂4 input = 𝐻2𝑆𝑂4 reacted + 𝐻2𝑆𝑂4 unreactedS

95 1281
= 10 (98) + 301 = 1281 = 𝑆 ( )→ 𝑆= = 1348 𝐼𝑏
100 0.95

5
Principles ch.10 Dr. Hameed R. Alamery

5
Water input = water output with (V) = 1348 ( ) = 67 𝐼𝑏
100
Composition of (V).
2
HF produced = 10 ( ) × 20 = 400 𝐼𝑏 HF = (400 / 467) X 100 =85.6 %
1
( )
∴ vapour V = 400 + 67 = 467 𝐼𝑏 H2O = (67 / 467) X 100= 14.4%

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈:
𝑰𝒏𝒑𝒖𝒕 = 𝑭 + 𝑺 = 𝟏𝟎𝟎𝟎 + 𝟏𝟑𝟒𝟖 = 𝟐𝟑𝟒𝟖 𝑰𝒃
𝑶𝒖𝒕𝒑𝒖𝒕 = 𝑹 + 𝑽 = 𝟏𝟖𝟖𝟏 + 𝟒𝟔𝟕 = 𝟐𝟑𝟒𝟖 𝑰𝒃

b.
Composition of (V).
H2SO4 input = 1281 Ib = (1281 / 98) = 13.07
CaF2 input = 10 Ib mole
𝟏𝟑.𝟎𝟕−𝟏𝟎
% 𝐞𝐱𝐜𝐞𝐬𝐬 𝑯𝟐 𝑺𝑶𝟒 = ( ) × 𝟏𝟎𝟎 = 𝟑𝟎. 𝟕 %
𝟏𝟎

6
 Principles ch.10 Dr. Hameed R. Alamery

Example 3:-
A solution of barium and calcium sulfides (F) is treated with commercial soda
ash (S) which consists of Na2CO3 and some impurities of CaCO3 in order to
produce barium carbonate according to the following reactions:
𝐵𝑎𝑆 + 𝑁𝑎2 𝐶𝑂3 → 𝐵𝑎𝐶𝑂3 ↓ + 𝑁𝑎2𝑆
M wt. 169.4 106 197.4 78
𝐶𝑎𝑆 + 𝑁𝑎2 𝐶𝑂3 → 𝐶𝑎𝐶𝑂3 ↓ + 𝑁𝑎2 𝑆
M wt. 72 106 100 78
Reaction product are separated by filtration. The precipitate (P) contains 9.9
wt. % CaCO3 & 90.1 wt. % BaCO3. The filtrate (T) contains 6.85 wt. % Na2S,
2.25 wt. % Na2CO3 and 90.9 wt. % H2O. The mass ratio between (P) & (T) is
16.45 Ib. / 100 Ib. Calculate the composition (wt. %) of (F) and (S).
Solution: S T
P T
Basis: 1000 Ib. of T 16.45 100
Reactor
F P
∴ mass of (P) = 164.5 Ib X 1000

90.1
Ba𝐶𝑂3 produced from 1 st. reaction = 164.5 ( ) = 148.2 𝐼𝑏
100
148.2
= = 0.751 𝐼𝑏𝑚𝑜𝑙𝑒
197.4
∴ 𝑁𝑎2 S produced from 1 st. reaction = 0.751 Ib mole =
0.751 (78) = 58.6 𝐼𝑏
6.85
Total 𝑁𝑎2 S produced from both reactions = 1000 ( ) = 68.5 Ib
100

∴ 𝑁𝑎2 S produced from 2 nd reactions = 68.5 − 58.6 = 9.9 Ib =

9.9
= 0.127 𝐼𝑏 𝑚𝑜𝑙𝑒
78
∴ 𝑁𝑎2 𝐶𝑂3 reacted in both reactions = 0.751 + 0.127 = 0.878 Ibmole
= 0.878 × 106 = 93.1 Ib
2.25
𝑁𝑎2 𝐶𝑂3 unreacted = 1000 ( ) = 22.5 Ib
100
∴ 𝑁𝑎2 𝐶𝑂3 input = 93.1 + 22.5 = 115.6 Ib

7
Principles ch.10 Dr. Hameed R. Alamery

Ca 𝐶𝑂3 produced from 2 nd reactions = 0.127 (100) = 12.7 Ib

9.9
Ca𝐶𝑂3 output with (P) = 164.5 ( ) = 16.3. 𝐼𝑏
100
Ca𝐶𝑂3 input with (S) = 16.3 − 12.7 = 3.6 𝐼𝑏

∴ S = 𝑁𝑎2 𝐶𝑂3 input + Ca𝐶𝑂3 input → S = 115.6 + 3.6 = 119.2 Ib

Composition of (S).
115.6
𝑁𝑎2 𝐶𝑂3 = × 100 = 96.98 %
119.2
3.6
Ca𝐶𝑂3 = × 100 = 3.02 %
119.2

Similarly:-

BaS reacted = BaS input = 0.751 Ibmole = 0.751 × 169.4 = 127.2 Ib

CaS reacted = CaS input = 0.127 Ibmole = 0.127 × 72 = 9.1 Ib

90.9
𝐻2 O input = 𝐻2 O output = 1000 ( ) = 909 Ib
100
∴ F = 𝐵𝑎𝑆 input + CaS input + 𝐻2O input →
F = 127.2 + 9.1 + 909 = 1045.3 Ib
Composition of (F).
BaS= (127.2 / 1045.3) X 100 =12.17 %
CaS = (9.1 / 1045.3) X 100= 0.87 %
H2O = 86.96 %

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈:
𝑰𝒏𝒑𝒖𝒕 = 𝑭 + 𝑺 = 𝟏𝟎𝟒𝟓. 𝟑 + 𝟏𝟏𝟗. 𝟐 = 𝟏𝟏𝟔𝟒. 𝟓 𝑰𝒃
𝑶𝒖𝒕𝒑𝒖𝒕 = 𝑻 + 𝑷 = 𝟏𝟎𝟎𝟎 + 𝟏𝟔𝟒. 𝟓 = 𝟏𝟏𝟔𝟒. 𝟓 𝑰𝒃

8
 Principles ch.10 Dr. Hameed R. Alamery

Example 4:-
Nitric acid can be manufactured by treading pure sodium nitrate (F) with
sulfuric acid solution (S) containing 95 wt. % H2SO4 according to the
reactions:
2𝑁𝑎𝑁𝑂3 + 𝐻2𝑆𝑂4 → 𝑁𝑎2 𝑆𝑂4 + 2𝐻𝑁𝑂3
M wt. 85 98.1 142.1 63
Most of HNO3 and H2O are volatilized and separated as vapour (V) from
residual niter cake (R) which contains 1.5 wt. % H2O, 34 wt. % H2SO4,
NaSO4 and 2 % of total HNO3 produced from reaction. On the basis of 1000
Ib of the (F), Calculate the quantities of S, V, R and the composition of (v) &
(R).
Solution: S
V
Basis: F= 1000 Ib. Reactor
F R

since no quantity of NaNO3 appears in V & R, thus all quantity input

are reacted, i. e. the reaction goes to completion
1000
∴ NaNO3 input = NaNO3 reacted = ( ) = 11.765 𝐼𝑏 𝑚𝑜𝑙𝑒
85
∴ H𝑁𝑂3 produced = 11.765 Ib mole = 11.765 (63) = 741 𝐼𝑏
2
H𝑁𝑂3 out with R = 741 ( ) = 14.8 𝐼𝑏
100
H𝑁𝑂3 out with V = 741 − 14.8 = 726.2 𝐼𝑏
1
∴ 𝑁𝑎2 𝑆𝑂4 produced = 11.765 ( ) (142.1) = 835.9 𝐼𝑏
2
64.5
(H𝑁𝑂3 + 𝑁𝑎2 𝑆𝑂4 )in R = 14.8 + 835.9 = 850.7 𝐼𝑏 = 𝑅 ( )
100

850.7 × 100 Composition of (R).

∴R= ( ) = 1318.9 𝐼𝑏
64.5 835.9
1.5 𝑁𝑎2 𝑆𝑂4 = × 100 = 63.4 %
1318.9
∴ 𝐻2O in R = 1318.9 ( ) = 19.8 𝐼𝑏
100 H𝑁𝑂3 =
14.8
× 100 = 1.1 %
34 1318.9
∴ 𝐻2𝑆𝑂4 in R = 1318.9 ( ) = 448.4 𝐼𝑏
100 𝐻2 O = 1.5 %,,,,,,,,𝐻2 𝑆𝑂4 = 34 %

9
Principles ch.10 Dr. Hameed R. Alamery

1
∴ 𝐻2𝑆𝑂4 reacted = 11.765 ( ) (98.1) = 577 𝐼𝑏
2

95
∴ 𝐻2 𝑆𝑂4 input = 448.4 + 577 = 1025.4 𝐼𝑏 = 𝑆 ( )
100
100
∴ 𝑆 = 1025.4 ( ) = 1079.4 𝐼𝑏
95
5
Water input = 1079.4 ( ) = 54 𝐼𝑏 = 𝑤𝑎𝑡𝑒𝑟 𝑜𝑢𝑡𝑝𝑢𝑡 𝑖𝑛 𝑅 & 𝑉
100
∴ water in (V) = 54 − 19.8 = 34.2 𝐼𝑏
Composition of (V).
∴ V = H𝑁𝑂3 in V + water in V
726.2
= 726.2 + 34.2 = 760.4 𝐼𝑏 H𝑁𝑂3 = × 100 = 95.5 %
760.4
34.2
𝐻2 O = × 100 = 4.5 %
760.4

𝑪𝒉𝒂𝒄𝒌𝒊𝒏𝒈:
𝑰𝒏𝒑𝒖𝒕 = 𝑭 + 𝑺 = 𝟏𝟎𝟎𝟎 + 𝟏𝟎𝟕𝟗. 𝟒 = 𝟐𝟎𝟕𝟗. 𝟒 𝑰𝒃
𝑶𝒖𝒕𝒑𝒖𝒕 = 𝑹 + 𝑽 = 𝟏𝟑𝟏𝟖. 𝟗 + 𝟕𝟔𝟎. 𝟒 = 𝟐𝟎𝟕𝟗. 𝟑 𝑰𝒃

10
 Principles ch.11 Dr. Hameed R. Alamery

Material balances Involving Combustion

Introduction:
Combustion is one of the most industrial processes commonly used for heat generation.
Fuels are burnt with oxygen, i.e air in such process to supply thermal energy to different
industrial process units.
Hence, combustion can be considered as process in which oxidation reaction take place. It
can be either “complete” or “incomplete”.
 Combustion is the reaction of a substance with oxygen with the associated release
of energy and generation of product gases such as H2O, CO2, CO, and SO2.
 Most combustion processes use air as the source of oxygen. For our purposes you
can assume that air contains 79% N2 and 21% O2.

Complete Combustion Process:-

If all carbon, hydrogen and selphur of the fuel are converted to CO2, H2O and SO2
respectively, the combustion is termed “Complete”.
Incomplete or Partial Combustion Process:-
If parts of the fuel remain unburned, or CO gaseous with product gases, the combustion is
termed “incomplete” or “partial combustion”.
Note that
 The reaction of S with O2 yield SO2 and SO3. Conversion of S to SO3 requires
specific conditions. Hence, it is customary to regard the conversion of all S to SO3
as complete union for stoichiometric calculations.
 The quantity of heat produced from complete combustion of any fuel is higher than
that produced from incomplete combustion. Theoretical quantity of oxygen required
for any combustion process is computed on the assumption of complete combustion.
The three general constituents of any combustion process are 1- fuel 2- air and 3- the stack
or flue gas. However, ash, or noncombustible material are included with solid fuel only.
1. FULE:-
The fuel used in power plant combustion furnaces may be solids, liquids, or gases.
A. Solid fuels: Principally coal is the most important classical and natural fuel. It
consists of 1- elemental carbon; 2- complex hydrocarbons of unknown saturate
consists of C, H, O, N, and S. 3- noncombustible matter that forms the ash.
B. Liquid fuel: Principally hydrocarbons obtained distillation of crude oil such as
gasoline, kerosene, diesel oil and fuel oil. However, there is growing interest to use
alcohols obtained by fermentation of grains as liquid fuel.

1
Principles ch.11 Dr. Hameed R. Alamery

C. Gaseous fuel: Principally natural gas is an imported gaseous fuel. It consists of

80 -95 % CH4 the remainder being ethane, propane and small quantities of other
gases. However, light hydrocarbons obtained from petroleum or coal treatment such
as procedure gas, blast-furnace gas and refinery gas are examples of synthetic
gaseous fuels. Acetylene and hydrogen can be also used as fuel but their production
are relatively expansive.

2. Air:
Air is the source of oxygen in most combustion processes for obvious economic
reasons. Air has the fallowing composition:
Mol. % Mol. % Mol. % Mol. %
N2= 78.03 O2 = 20.99 Ar = 0.94 CO2 = 0.03
H2, He, Ne, Kr, Xe. = 0.01 mol%
Total = 100 %
Average molecular weight = 29.0
The volume of 1 Ibmole under 77 °F & 1 atm. is equal to 392 ft3

However, combustion calculators are usually carried out with composition of 79%
N2 and 21% O2 to simplify such calculations.
Theoretical air or (theoretical oxygen):
It is the quantity of air (or oxygen) required to burn the fuel completely according
to the stoichiometric requirement so that all C, H, and S are converted to CO2,
H2O and SO2 respectively.
Excess Air (or excess oxygen):
In actual practice, theoretical air is not sufficient to get complete combustion,
hence, excess amount of air is usually supplied. It is defined as fallowing
𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = 𝑎𝑐𝑡𝑢𝑎𝑙 𝑎𝑖𝑟 𝑖𝑛𝑝𝑢𝑡 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑎𝑖𝑟
𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 𝑎𝑐𝑡𝑢𝑎𝑙 𝑖𝑛𝑝𝑢𝑡 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑖𝑟
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100 = × 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑖𝑟 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑖𝑟

% excess air may be also computed as:

𝑎𝑐𝑡𝑢𝑎𝑙 𝑂2 𝑖𝑛𝑝𝑢𝑡 − 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2

2
 Principles ch.11 Dr. Hameed R. Alamery

It is important to note that heat losses through the fuel Excess air for fuels
gases increases with increasing % excess air, hence, it Fuels % Excess air
is better to choose the optimum value of % excess air
Solids 25 to 60
depending type of the fuel as given in the following
table. Liquids 15 to 35
Gases 10 to 20

3 Stack or flue Gases::

The product gases where are proceed from combustion reactions including the water
vapour is known as the “stack or flue gas” since it leaves the combustion chamber
and has been evolved to the atmosphere through the stack. Normally, flue gases contain
CO2, CO, O2, N2, and H2O.
The most common method used for flue gas analyses is by “Orsat analyses” The Orsat
apparatus was originally patent in 1873 by Orsat, and was modify later by a number of
investigators. It is based on passing measured volume (usually 100 Cm3) of a dry
sample of a flue gas on a series of absorbents and successively measured the reduction
in volume of sample.
Note: water vapour does not appear in the Orsat analysis since it is eliminated from the
flue gas before analysis measurements, hence analysis by this method is on “dry basis”
Flue or stack gas analysis (Wet basis)
CO2 CO O2 N2 H2O
Dry flue gas Orsat analysis or (dry basis)
CO2 CO O2 N2

Schematic diagram of Orsat analysis and

analysis procedure are as follow:

3
 Principles ch.11 Dr. Hameed R. Alamery

Special terms:
1. Flue or stack gas: All the gases resulting from combustion process including the
water vapor, sometimes known as a wet basis.
2. Orsat analysis or dry basis: All the gases resulting from combustion process not
including the water vapor. Orsat analysis refers to a type of gas analysis apparatus
in which the volumes of the respective gases are measured over and in equilibrium
with water; hence each component is saturated with water vapor. The net result of
the analysis is to eliminate water as a component being measured (show Figure
10.4).
3. Complete combustion: the complete reaction of the hydrocarbon fuel producing
CO2, SO2, and H2O.
4. Partial combustion: the combustion of the fuel producing at least some CO.
Because CO itself can react with oxygen, the production of CO in a combustion
process does not produce as much energy as it would if only CO2 were produced.
5. Theoretical air (or theoretical oxygen): The minimum amount of air (or oxygen)
required to be brought into the process for complete combustion. Sometimes this
quantity is called the required air (or oxygen).
6. Excess air (or excess oxygen): In line with the definition of excess reactant given
in Chapter 9, excess air (or oxygen) would be the amount of air (or oxygen) in excess
of that required for complete combustion as defined in (5).
Note: The calculated amount of excess air does not depend on how much material is actually
burned but what is possible to be burned. Even if only partial combustion takes place, as,
for example, C burning to both CO and CO2, the excess air (or oxygen) is computed as if
the process of combustion went to completion and produced only CO2 .
The percent excess air is identical to the percent excess O2:
𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2⁄
% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100 = 0.21 × 100 … … … … . . (1)
𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑎𝑖𝑟 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑂2⁄
0.21
O2 AIR
1
𝒆𝒙𝒄𝒆𝒔𝒔 𝒂𝒊𝒓 = 𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2 × 0.21
Excess O2 excess air
0.21 1

Note that the ratio 1/0.2 1 of air to O2 cancels out in Equation (1) Percent excess air may
also be computed as

𝑂2 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 − 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑

% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100 … … … … . . (2)
𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑

𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2
𝑂𝑅 % 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100 … … … .. (3)
𝑂2 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 − 𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2

4
Principles ch.11 Dr. Hameed R. Alamery

Material balance ((Combustion)):- ‫االحتراق‬

Fuel Burner Flue

AIR

79 mol. %N2

21 mol. %O2

: Wet flue gas, stock gas, flue

Co2 ,Co ,O2 ,N2 ,So2 , H2o ‫كل الغازات الخارجة من االحتراق‬
Ash, impurities
: Orsate analysis, dry flue gas
H2o ‫كل الغازات الخارجة من االحتراق ولكن بدون‬

𝑰𝒏 − 𝒕𝒉𝒆𝒐.
% 𝒆𝒙𝒄𝒆𝒔𝒔 = × 𝟏𝟎𝟎
𝒕𝒉𝒆𝒐.
.‫ لحرق الوقود بشكل كامل‬O2 ‫ الكمية النظرية الواجب توفيرها من‬Theo. 
. ‫) فقط في معادلة االحتراق التام‬in ‫ مع‬in( ‫ يمكن ايجاده من المقارنة‬Theo. 

5
 Principles ch.11 Dr. Hameed R. Alamery

Example 11.1 Excess Air

Fuels for motor vehicles other than gasoline are being eyed because they generate lower
levels of pollutants than does gasoline. Compressed propane has been suggested as a source
of economic power for vehicles. Suppose that in a test 20 kg of C3H8 is burned with 400
kg of air to produce 44 kg of CO2 and 12 kg of CO. What was the percent excess air?

Solution:
This is a problem involving the following reaction (is the reaction equation correctly
balanced?)

𝐶3 𝐻8 + 5 𝑂2 → 3𝐶𝑂2 + 4𝐻2 𝑂
Basis: 20 kg of C3H8
Since the percentage of excess air is based on the complete combustion of C3H8 to CO2
and H2O, the fact that combustion is not complete has on influence on the definition of
“excess air “. The required O2 is
20 kg C3H8 1 kg mol. C3H8 5 kg mol. O2 = 2.27 kg mol.
C3H8 O2
44.09 kg C3H8 1 kg mol. C3H8 O2
1 5
The entering O2 is 0.453 X
400 kg air 1 kg mol. air 21 kg mol. O2 = 2.90 kg mol. O2
29 kg air 100 kg mol. air Air O2

100 21
The percentage excess air is
20 X
𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 𝑂2 − 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑂2
× 100 = × 100
𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑂2

2.90 𝑘𝑔 𝑚𝑜𝑙 𝑂2 − 2.27 𝑘𝑔 𝑚𝑜𝑙 𝑂2

% 𝑒𝑥𝑐𝑒𝑠𝑠 𝑎𝑖𝑟 = × 100 = 28 %
2.27 𝑘𝑔 𝑚𝑜𝑙 𝑂2

6
 Principles ch.11 Dr. Hameed R. Alamery

Example 11.2
Methane is completely burned with 26 % excess air. Calculate:
A// the Orsat analysis of the flue gas.
B// the molal ratio of water vapour to the dry flue gas, and.
C// the molal ratio of air to methane.
Solution:

𝐶𝐻4 + 2 𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂

Basis: 100 Ib mole of CH4

∴ 𝑇ℎ𝑒𝑜. 𝑂2 = 200 𝐼𝑏 𝑚𝑜𝑙𝑒 CH4 O2

26 1 2
𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2 = 200 ( ) = 52 𝐼𝑏 𝑚𝑜𝑙𝑒
100 100 X

𝐴𝑐𝑡𝑢𝑎𝑙 𝑂2 𝑖𝑛𝑝𝑢𝑡 = 252 𝐼𝑏 𝑚𝑜𝑙𝑒

N2 O2
79 𝑁2
𝑁2 𝑖𝑛𝑝𝑢𝑡 = 252 𝑂2 ( ) = 948 𝐼𝑏 𝑚𝑜𝑙𝑒 79 21
21 𝑂2
X 254
𝐶𝐻4 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 𝐶𝐻4 𝑖𝑛𝑝𝑢𝑡 = 100 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 100 (2) = 200 𝐼𝑏 𝑚𝑜𝑙𝑒
𝐶𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 100 = 100 𝐼𝑏 𝑚𝑜𝑙𝑒
𝐻𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 200 = 200 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑶𝟐 𝒖𝒏𝒓𝒆𝒂𝒄𝒕𝒆𝒅 = 𝟓𝟐 𝑰𝒃 𝒎𝒐𝒍𝒆
Orsat analysis
CO2 100 9.1%
O2 52 4.7 %
N2 948 86.2 %
1100 100 %
𝑊𝑎𝑡𝑒𝑟 𝑣𝑎𝑝. 200 2 18.2 𝑚𝑜𝑙 𝐻2𝑂
( )= = = 0.182: 1 =
𝑑𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠 1100 11 100 𝑚𝑜𝑙 𝑑𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠
𝐴𝑖𝑟 𝑖𝑛𝑝𝑢𝑡 = 252 𝑂2 + 948 𝑁2 = 1200 𝐼𝑏 𝑚𝑜𝑙𝑒
𝐴𝑖𝑟 1200
= = 12 ∶ 1
𝐶𝐻4 100

7
 Principles ch.11 Dr. Hameed R. Alamery

Example 11.3
A gaseous fuel composed of 80 mol. % CH4, 10 mol. % H2, 10 mol. %N2 is burned with
40 % excess air. 80 %of the carbon burned goes to CO2, the rest convert to CO, and all
hydrogen are converted to H2O. Calculate: A// the molal ratio of air input to the fuel burned.
B// Orsat analysis of the flue gas, and C// molal ratio of water vapour to the dry flue gas.
Solution:
Basis: 100 Ib mole of the fuel.
CH4 = 80 Ib mole H2 = 10 Ib mole N2 = 10 Ib mole

𝐶𝐻4 + 2 𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 Theoretically

80 assumed
𝐻2 + 1/2 𝑂2 → 𝐻2 𝑂 complete
10 combustion

1
∴ 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 80(2) + 10 ( ) = 165 𝐼𝑏 𝑚𝑜𝑙𝑒
2
40
𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2 = 165 ( ) = 66 𝐼𝑏 𝑚𝑜𝑙𝑒
100

𝐴𝑐𝑡𝑢𝑎𝑙 𝑂2 𝑖𝑛𝑝𝑢𝑡 = 165 + 66 = 231 𝐼𝑏 𝑚𝑜𝑙𝑒

100 Air O2
𝐴𝑖𝑟 𝑖𝑛𝑝𝑢𝑡 = 231 ( ) = 1100 𝐼𝑏 𝑚𝑜𝑙𝑒
21
100 21
𝐴𝑖𝑟 1100
∴ = = 11 ∶ 1 X 231
𝐹𝑢𝑒𝑙 100
𝑁2 𝑖𝑛𝑝𝑢𝑡 𝑤𝑖𝑡ℎ 𝐹𝑢𝑒𝑙 + 𝑁2 𝑖𝑛𝑝𝑢𝑡 𝑤𝑖𝑡ℎ 𝐴𝑖𝑟 = 𝑁2 𝑜𝑢𝑡𝑝𝑢𝑡
79
𝑁2 𝑜𝑢𝑡𝑝𝑢𝑡 = 10 + 1100 ( ) = 869 𝐼𝑏. 𝑚𝑜𝑙𝑒 Air N2
100
100 79
1100 X

8
Principles ch.11 Dr. Hameed R. Alamery

𝐶𝐻4 + 2 𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 Actual reaction

64 80
𝐶𝐻4 𝑔𝑜𝑒𝑠 𝑡𝑜 𝐶𝑂2 = 80 ( ) = 64 𝐼𝑏. 𝑚𝑜𝑙𝑒
100
𝐶𝐻4 + 3/2 𝑂2 → 𝐶𝑂 + 2𝐻2 𝑂 20
𝐶𝐻4 𝑔𝑜𝑒𝑠 𝑡𝑜 𝐶𝑂 = 80 ( ) = 16 𝐼𝑏. 𝑚𝑜𝑙𝑒
16 100
𝐻2 + 1/2 𝑂2 → 𝐻2 𝑂
10

∴ 𝐶𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 64 𝐼𝑏 𝑚𝑜𝑙𝑒

𝐶𝑂 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 16 𝐼𝑏 𝑚𝑜𝑙𝑒
∴ 𝐻𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 64(2) + 16 (2) + 10 = 170 𝐼𝑏 𝑚𝑜𝑙𝑒
1
∴ 𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 64(2) + 16 (1.5) + 10( ) = 157 𝐼𝑏 𝑚𝑜𝑙𝑒
2
𝑂2 𝑜𝑢𝑡𝑝𝑢𝑡 = 𝑂2 𝑖𝑛𝑝𝑢𝑡 − 𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 231 − 157 = 74 𝐼𝑏 𝑚𝑜𝑙𝑒

Orsat analysis
Component Ib. mole Mol. %
CO2 64 6.2%
CO 16 1.5 %
N2 879 85.1 %
O2 74 7.2
Total 1033 100 %

𝐻2𝑂 170 0.165 𝑚𝑜𝑙 𝐻2𝑂

= =
𝐷𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠 1033 𝑚𝑜𝑙 𝑑𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠

9
 Principles ch.11 Dr. Hameed R. Alamery

Example 11.4
A liquid fuel consists of 36 mol. % Pentane (C5H12) and 64 mol. % Hexane (C6H14) is
burned with 20 % excess air. 80 % of the carbon goes to CO2 and 20 % goes to CO.
Calculate the Orsat analysis of the stack gas and the molal ratio of water vapour to the dry
flue gas.
Solution:
Basis: 100 Ib mole of the fuel.
C5H12 = 36 Ib mole C6H14 = 64 Ib mole

𝐶5 𝐻12 + 8 𝑂2 → 5 𝐶𝑂2 + 6𝐻2 𝑂 Theoretically

36 assumed
𝐶6 𝐻14 + 9.5 𝑂2 → 6 𝐶𝑂2 + 7𝐻2 𝑂 complete
64 combustion

∴ 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 36(8) + 64(9.5) = 896 𝐼𝑏 𝑚𝑜𝑙𝑒

20
𝑒𝑥𝑐𝑒𝑠𝑠 𝑂2 = 896 ( ) = 179 𝐼𝑏 𝑚𝑜𝑙𝑒
100

𝐴𝑐𝑡𝑢𝑎𝑙 𝑂2 𝑖𝑛𝑝𝑢𝑡 = 896 + 179 = 1075 𝐼𝑏 𝑚𝑜𝑙𝑒

79 𝑁2
𝑁2 𝑖𝑛𝑝𝑢𝑡 = 1075 𝑂2 ( ) = 4044 𝐼𝑏 𝑚𝑜𝑙𝑒 = 𝑁2 𝑜𝑢𝑡𝑝𝑢𝑡
21 𝑂2
∴ 𝐴𝑖𝑟 𝑖𝑛𝑝𝑢𝑡 = 1075 + 4044 = 5119 𝐼𝑏 𝑚𝑜𝑙𝑒
Method 1
𝐶5 𝐻12 + 8 𝑂2 → 5 𝐶𝑂2 + 6𝐻2 𝑂
80
36 ( ) = 28.8 𝐼𝑏 𝑚𝑜𝑙𝑒
100
𝐶5 𝐻12 + 5.5 𝑂2 → 5 𝐶𝑂 + 6𝐻2 𝑂
20
36 ( ) = 7.2 𝐼𝑏 𝑚𝑜𝑙𝑒 Actual reaction
100
𝐶6 𝐻14 + 9.5 𝑂2 → 6 𝐶𝑂2 + 7𝐻2 𝑂
80
64 ( ) = 51.2 𝐼𝑏 𝑚𝑜𝑙𝑒
100
𝐶6 𝐻14 + 6.5 𝑂2 → 6 𝐶𝑂 + 7𝐻2 𝑂

10
Principles ch.11 Dr. Hameed R. Alamery

20
64 () = 12.8 𝐼𝑏 𝑚𝑜𝑙𝑒
100
∴ 𝐶𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 5(28.8) + 6 (51.2) = 451 𝐼𝑏 𝑚𝑜𝑙𝑒
𝐶𝑂 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 5 (7.2) + 6 (12.8) = 113 𝐼𝑏 𝑚𝑜𝑙𝑒
∴ 𝐻𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 6(28.2 + 7.2) + 7 (51.2 + 12.8) = 216 + 447
= 664 𝐼𝑏. 𝑚𝑜𝑙𝑒
∴ 𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 8(28.8) + 5.5 (7.2) + 9.5 (51.2 + 6.5(12.8)
= 230.4 + 39.6 + 486.4 + 83.2 = 840 𝐼𝑏. 𝑚𝑜𝑙𝑒
𝑂2 𝑜𝑢𝑡𝑝𝑢𝑡 = 1075 − 840 = 235 𝐼𝑏 𝑚𝑜𝑙𝑒
𝐻2𝑂 664 0.137 𝑚𝑜𝑙 𝐻2𝑂
= =
𝐷𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠 4843 𝑚𝑜𝑙 𝑑𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠

Method 2
Component Ib. mole Ib. mole C Ib. mole H2

C5H12 36 5 X 36= 180 6 X 36= 216

C6H14 64 6 X 64= 384 7 X 64= 448
Total 100 564 664

𝐶 + 𝑂2 → 𝐶𝑂2
80
564 ( ) = 451 𝐼𝑏 𝑚𝑜𝑙𝑒
100
𝐶 + 1/2 𝑂2 → 𝐶𝑂
20
564 ( ) = 113 𝐼𝑏 𝑚𝑜𝑙𝑒
100
𝐻2 + 1/2 𝑂2 → 𝐻2 𝑂
664

∴ 𝐶𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 451 𝐼𝑏 𝑚𝑜𝑙𝑒

𝐶𝑂 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 113 𝐼𝑏 𝑚𝑜𝑙𝑒
11
Principles ch.11 Dr. Hameed R. Alamery

∴ 𝐻𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 664 𝐼𝑏. 𝑚𝑜𝑙𝑒

113 664
∴ 𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 451 + + = 840 𝐼𝑏. 𝑚𝑜𝑙𝑒
2 2
Orsat analysis
Component Ib. mole Mol. %
CO2 451 9.31%
CO 113 2.34 %
N2 4044 82.5 %
O2 235 4.89
Total 4843 100 %

12
 Principles ch.11 Dr. Hameed R. Alamery

Example 11.5
A fuel composed of carbon and hydrogen is burned with dry air. The Orsat analysis of the
flue gas are as follow: CO2 5.4 %, O2 7.7 %, N2 86.9 %. Calculate:
A// Ib mole of air used per 100 Ib. mole of the dry flue gas. B// % excess air?
C// Ib mole of H2O used per 100 Ib. mole of the dry flue gas.
D//The mass ratio of carbon to hydrogen the fuel and
E//Ib. mole of the flue gas produced from burning 1 Ib. of the fuel.
Solution:
A// Basis: 100 Ib mole of dry flue gas

CO2 = 5.4 Ib mole O2 = 7.7 Ib mole N2= 86.9 Ib mole

𝑁2 𝑖𝑛𝑝𝑢𝑡 = 𝑁2 𝑜𝑢𝑡𝑝𝑢𝑡 = 86.9 𝐼𝑏 𝑚𝑜𝑙𝑒

N2 O2
21 𝑂2
𝐴𝑐𝑡𝑢𝑎𝑙 𝑂2 𝑖𝑛𝑝𝑢𝑡 = 86.9 𝑁2 ( ) = 23.1 𝐼𝑏 𝑚𝑜𝑙𝑒 79 21
79 𝑁2
86.9 X
∴ 𝐴𝑖𝑟 𝑖𝑛𝑝𝑢𝑡 = 86.9 + 23.1 = 110 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑖. 𝑒. 110 𝐼𝑏 𝑚𝑜𝑙𝑒 𝑎𝑖𝑟 ⁄100 𝐼𝑏 𝑚𝑜𝑙𝑒 𝑑𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠

B//
⋯ 𝑆𝑖𝑛𝑐𝑒 𝑛𝑜 𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑜𝑓 𝐶𝑂 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠, ℎ𝑒𝑛𝑐𝑒 𝑡ℎ𝑒𝑠𝑒 𝑖𝑠 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒 𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛

𝑖. 𝑒. 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2 = 𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑖. 𝑒. 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑂2 = 𝑂2 𝑖𝑛𝑝𝑢𝑡 − 𝑂2 𝑜𝑢𝑡𝑝𝑢𝑡 = 23.1 − 7.7 = 15.4 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑂2 𝐼𝑛 − 𝑂2 𝑡ℎ𝑒𝑜. 23.1 − 15.4
% 𝑒𝑥𝑐𝑒𝑠𝑠 = × 100 = × 100 = 50 %
𝑂2 𝑡ℎ𝑒𝑜. 15.4

13
 Principles ch.11 Dr. Hameed R. Alamery

C//
𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑤𝑖𝑡ℎ 𝐶 = 5.4 𝐼𝑏 𝑚𝑜𝑙𝑒 𝐶 + 𝑂2 → 𝐶𝑂2
𝑂2 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑤𝑖𝑡ℎ 𝐻2 = 15.4 − 5.4 = 10 𝐼𝑏 𝑚𝑜𝑙𝑒 2𝐻2 + 𝑂2 → 2𝐻2𝑂

∴ 𝐻2 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑢𝑙𝑒 = 10(2) = 20 𝐼𝑏 𝑚𝑜𝑙𝑒

𝐻𝑂2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 20 𝐼𝑏 𝑚𝑜𝑙𝑒 → 𝑖. 𝑒. 20 𝐼𝑏 𝑚𝑜𝑙𝑒⁄100 𝐼𝑏 𝑚𝑜𝑙𝑒 𝑑𝑟𝑦 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠

D//
𝑾 𝟓. 𝟒 × 𝟏𝟐 𝟔𝟒. 𝟖
𝒊. 𝒆. 𝒄𝒂𝒓𝒃𝒐𝒏⁄𝒉𝒚𝒅𝒓𝒐𝒈𝒆𝒏 ( ) 𝒓𝒂𝒕𝒊𝒐 = ( )=( ) = 𝟏. 𝟔𝟐
𝑾 𝟐𝟎 × 𝟐 𝟒𝟎

E//
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶 + 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐻
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑓𝑢𝑒𝑙 = 64.8 + 40 = 104.8 𝐼𝑏
𝑚𝑜𝑙𝑒 𝑜𝑓 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠 = 100 + 20 = 120 𝐼𝑏 𝑚𝑜𝑙𝑒

120 𝐼𝑏 𝑚𝑜𝑙 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠

𝑚𝑜𝑙𝑒 𝑓𝑙𝑢𝑒 𝑔𝑎𝑠 ⁄𝐼𝑏 𝑓𝑢𝑒𝑙 = ( ) = 1.145
104.8 𝐼𝑏 𝑓𝑢𝑒𝑙

Ib fuel Ib. mole flue gas

104.8 120
1 X

14
 Principles ch.12 Dr. Hameed R. Alamery

Material balance on processes involving

Recycle, by pass and purge streams

Introduction:
Recycle, by pass and purge streams are commonly used in the design of chemical processes
around the reaction units (reactors) as well as in unit operations such as drying, distillation
and extraction units. Typical materials balance calculations on processes involving such
streams are given in this section.

(A): Recycle Stream:

It is part of the product stream (either of similar or different composition ) that is separated
and returned to mix again with inlet stream (fresh feed ) for economic considerations .The
gross product (G) leaving the process is commonly separated by suitable separation
technique such as distillation, filtration, extraction …………etc. into the net product (P)
and the recycle stream (R); whereas the total feed (T) input to the process is made up by
mixing the fresh feed (F and the recycle stream (R) as shown in the following block
diagram.
Recycle stream(R)
1
2 3 4
F T PROCESS G P
MIXER SEPARATO
R

Fresh Feed Total Feed Gross Product Net Product

The recycle ratio; sometimes called reflux ratio, is widely used in recycle calculations. It
𝑹
is the ratio between the amount of recycle to that of the net product, i.e. (𝑷).

Material balance calculations can be made around (1) the entire process, (2) the mixing
unit (3) the process only, and (4) separation unit.
The sequence of calculation steps depends on the data given in the problem.
∗Note: that the quantity of net product depends only on the charged once at the starting
period of working the process and remains circulated inside the process with constant flow
rate and composition under steady state condition and it is fixed according to economic
considerations

1
 Principles ch.12 Dr. Hameed R. Alamery

Some of important aims and applications of recycling operation are as follow.

1. To recovery and avoid wastage of catalyst and unconverted substances for
processes involving chemical reactions of lower percent conversion of
reactants.
‫الستعادة وتجنب إهدار العامل المساعد والمواد غير المتحولة‬
2. To utilize the heat being lost in the outgoing stream such as recycling part of
the hot wet air that leaves the drying unit to mix with the fresh feed of add dry
air.
‫االستفادة من الحرارة المفقودة في التيار الخارج‬
3. To maintain the required conditions to perform the process with higher
efficiency such as recycling part of the top product in rectification distillation
from the top of the column with vapour from the bottom of the column in order
to separate the components by gas liquid mass transfer operation.
R
Reflux ratio ( ) is the most important parameter in the design of distillation
D
column so that the cost is directly dependent on this parameter.
‫للحفاظ على الشروط المطلوبة ألداء العملية بكفاءة أعلى‬
4. To dilute the fresh feed such as recycling part of filtrate that leaves filtrations
unit to mix with fresh slurry since it is difficult to handle slurry with high solid
concentration and the filter will operate more properly with recycle.

5. To improve the selectivity of the desired product.

(B) By pass Stream:

It is a fraction of the fresh feed that skips once or more stages of the process and
goes directly to another stage in parallel with other fraction of the feed that
passes through the process as shown in the following block diagram. This
arrangement is used when it is desired to make a relatively small change in the
feed stream or to control the composition of product at desired value.
Bypass

Fresh feed Product

Divider Process Mixer

Some of important applications of bypass stream are as follow

1. Pumping of liquid from a storage tank by a more efficient pump of high
horsepower to a small process unit at desired lower flow rate.
2. Dissolution of caustic soda in water by a two steps process to the very high
heat of dissolution.

2
 Principles ch.12 Dr. Hameed R. Alamery

3. Separation of mixtures by a more efficient distillation column, so that a bypass

stream is used to control the composition of the final product at the desired
value.

(C) Purge stream:

It is fraction of the recycle stream (with the same composition ) that is removed out the
process to prevent accumulation of inert materials (that are not involve in the reaction ) in
the recycle stream so that the quantity of inert input with the fresh feed is equal to that
output with purge stream as shown in the following block diagram .
‫شكراش‬
Recycle (R) Purge (G)
Divider

(F) Fresh feed (P) product

Mixer Process Separato
r
F (wt. fraction of inert in F) = G (wt. fraction of inert in G) = G (wt. fraction of inert in R)

[Since: G & R have the same composition]

The important example of application of purge stream is in the production of ammonia
from gaseous mixture of N2 & H2 containing some impurities of argon as shown in the
following block diagram.

Purge stream
(H2, N2, Air)

Reactor Condenser
(H2, N2, Air)
NH3
Similarly, purge stream is used in the process of acetaldehyde production by oxidation of
ethylene according to the reaction:

2 𝐶2 𝐻4 + 𝑂2 → 2𝐶2 𝐻4 O

3
 Principles ch.12 Dr. Hameed R. Alamery

The feed to the process consists of ethylene and air and conversion of C2H4 is about 50 %,
hence, nitrogen input with air must be removed by purge stream in order to return unreacted
C2H4 as a recycle stream.

Recycle, by pass and Purge Streams

Example 1:

A binary mixture consists of 45 Wt.% benzene and 55 Wt.% toluene are continuously fed
to distillation column at a rate of 2500 Ib / hr .The Top product contains 97.5 Wt.%
benzene, whereas the bottom product contains 90 Wt.% toluene The column operate with
reflux ratio of 2.5.

Calculate: A// the top & bottom products produced per hour

B// the recycle stream and the vapor input to the condenser per hour

Solution:
Condenser

V
Divider
R
F = 2500 Ib. / hr. D
Distillation 97.5 % benzene
45 % benzene Column 2.5 % toluene
55 % toluene

10 % benzene
90 % toluene
W

Re boiler

A// Basis: 1 hr. ≡ 2500 Ib. of F

1- Material balance overall the process

𝑇. 𝑀. 𝐵 F = 𝐷 + 𝑊 → 𝐷 + 𝑊 = 2500 … … … … (1)

4
 Principles ch.12 Dr. Hameed R. Alamery

Benzene balance
𝐹 𝑋𝐹 = 𝐷 𝑋𝐷 + 𝑊 𝑋𝑊
2500 (0.45) = 𝐷 (0.975) + 𝑊 (0.1) → 1125 = 0.975 𝐷 + 0.1 𝑊 … … . . (2)
(Sub. 1 in 2) 1125 = 0.975 𝐷 + 0.1 ( 2500 − 𝐷)

875
875 = 0.875 𝐷 → 𝐷= = 1000 Ib/hr
0.875

(Sub. in 1) 𝑊 = 2500 − 1000 = 1500 𝐼𝑏/ℎ𝑟

Checking
Toluene balance:
𝟓𝟓
𝐓𝐨𝐥𝐮𝐞𝐧𝐞 𝐢𝐧𝐩𝐮𝐭 = 𝐅 ( ) = 𝟐𝟓𝟎𝟎 (𝟎. 𝟓𝟓) = 𝟏𝟑𝟕𝟓 𝑰𝒃
𝟏𝟎𝟎
𝟐. 𝟓 𝟗𝟎
𝐓𝐨𝐥𝐮𝐞𝐧𝐞 𝐨𝐮𝐭𝐩𝐮𝐭 = 𝐃 ( )+𝑾( ) = 𝟏𝟎𝟎𝟎(𝟎. 𝟎𝟐𝟓) + 𝟏𝟓𝟎𝟎(𝟎. 𝟗) = 𝟏𝟑𝟕𝟓 𝑰𝒃
𝟏𝟎𝟎 𝟏𝟎𝟎

B// 2. Material balance on Divider

𝑇. 𝑀. 𝐵 V = 𝑅 + 𝐷 … … … … (3)
𝑅
Reflux ratio = = 2.5 → ∴ R = 2.5 D = 2.5 (1000) = 2500 Ib/hr
𝐷

(Sub. in 3) 𝑉 = 2500 + 1000 = 3500 𝐼𝑏/ℎ𝑟

5
 Principles ch.12 Dr. Hameed R. Alamery

Example 2:
Soybean slakes (S) containing 19 wt.% oil & 81 wt.% solids are continuously fed at rate
of 5000 kg /hr. to the vegetable oil production process in which soybean oil are extracted
by hence as show in the following block diagram

The filter cake (C) contains 90 wt. % solids &10 wt. % liquid of hexane +oil of the same
composition of the filtrate (F). Calculate:

(a) The flow rates in kg/hr. of all streams of the process and the composition of (M) &
(E).
(b) Yield of the process

Recycle (R)
4 % oil
96 % hexane

M E Filtrate (F) Distillation

Mixer Extractor Filter
20 % oil
Column
80% hexane

Hexane (H)
(S) Soybean flakes Cake (C)

Product (P)
Solution: Basis: 1 hr. ≡ 5000 kg of (S) 100 % oil
CH3CHO
Calc. the composition of (C)
1. Material balance overall the process
Basis 100kg of C
(a) solid balance
81 90 Solid in C = 90 kg
𝑆( ) = 𝐶( )
100 100
Liquid in C = 10 kg
5000 (0.81) = 0.9 𝐶 → 𝐶 = 4500 𝐾𝑔/ℎ𝑟 % of liq. = 20 % oil & 80 % hexane
(b) hexane balance
Oil = 10 (20/100) = 2 kg
8 8
𝐻 = 𝐶( ) → 𝐻 = 4500 ( ) Hexane = 10 (80/100) = 8 kg
100 100
= 360 𝑘𝑔/ℎ𝑟 i.e. 2% oil & 8% hexane and 90% solid

6
Principles ch.12 Dr. Hameed R. Alamery

(c) oil balance

19 2 kg
S( )= P+ C ( ) → P = 950 – 90 = 860
100 100 hr
Checking:
𝐢𝐧𝐩𝐮𝐭 = 𝐒 + 𝐇 = 𝟓𝟎𝟎𝟎 + 𝟑𝟔𝟎 = 𝟓𝟑𝟔𝟎 𝒌𝒈/𝒉𝒓
𝐨𝐮𝐭𝐩𝐮𝐭 = 𝐂 + 𝑷 = 𝟒𝟓𝟎𝟎 + 𝟖𝟔𝟎 = 𝟓𝟑𝟔𝟎 𝒌𝒈/𝒉𝒓

𝑃𝑟𝑜𝑑𝑢𝑐𝑡 860 𝑘𝑔 𝑂𝑖𝑙

𝐘𝐢𝐞𝐥𝐝 = = = 0.172 kgoil /kg soybean
𝐹𝑒𝑒𝑑 5000 𝑘𝑔 𝑆𝑜𝑦𝑏𝑒𝑎𝑛

2. Material balance on distillation

a. Oil balance
0.2 𝐹 = 𝑃 + 0.04 𝑅 = 860 + 0.04𝑅 … … … … … … … (1)
b. Hexane balance

0.8 𝐹 = 0.96 𝑅 … … … … … . (2)

(𝐒𝐮𝐛. 𝟏 𝐢𝐧 𝟐) 𝑅 = 4300 𝑘𝑔/ℎ𝑟 𝑎𝑛𝑑 𝐹 = 5160 𝑘𝑔/ℎ𝑟

3. Material balance on Mixer

𝑀 = 𝑅 + 𝐻 → 𝑀 = 4300 + 360 = 4660 𝑘𝑔/ℎ𝑟

4300 (0.04)
𝐶𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑜𝑓 𝑀 𝑂𝑖𝑙 = ( ) × 100 = 3.69 %
4660

360 + 4300 (0.96)

𝐻𝑒𝑥𝑎𝑛𝑒 = ( ) × 100 = 96.31 %
4660
4. Material balance on Extractor
𝐸 = 𝑀 + 𝑆 → 𝐸 = 4660 + 5000 = 9660 𝑘𝑔/ℎ𝑟
Oil in E 172+ 950 = 1122 kg 11.6%
0.04 R + oil in S= 1122
Kg
Hexane in E 4488 kg 46.5%
0.96 R + H =
Solid in E 4050 kg 41.9%
Soild in S
Total 9660 kg 100 %

5. Final checking (material balance on filter)

Checking:
𝐢𝐧𝐩𝐮𝐭 = 𝐄 = 𝟗𝟔𝟔𝟎 𝒌𝒈/𝒉𝒓
𝐨𝐮𝐭𝐩𝐮𝐭 = 𝐅 + 𝑪 = 𝟓𝟏𝟔𝟎 + 𝟒𝟓𝟎𝟎 = 𝟗𝟔𝟔𝟎 𝒌𝒈/𝒉𝒓

7
 Principles ch.12 Dr. Hameed R. Alamery

Example 3:
Acetaldehyde (CH3CHO) is produced at rate of 1100 Ib/hr (P) by catalytic dehydrogenation
of ethanol:

𝐶2 𝐻5 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻𝑂 + 𝐻2

𝑀 𝑤𝑡. 46 44 2

It is found that 80% of ethanol input to the reactor are converted, and the rest are completely
recycled. Calculate the mass flow rate of fresh ethanol (F), recycle stream (R), and
hydrogen evolved (G).

(R) C2H5OH recycle

G H2

F CH5OH
Mixer Reactor Separator

Solution: Basis: 1 hr ≡ 1100 Ib. of (P) P =1100 Ib/hr

CH3CHO
1100
𝐶𝐻3 CHO produced = = 25 𝐼𝑏𝑚𝑜𝑙𝑒
44

𝐻2 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 25 𝐼𝑏𝑚𝑜𝑙𝑒 → 𝐺 = 25 (2) = 50 𝐼𝑏/ℎ𝑟

𝐶2 𝐻5 𝑂𝐻 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = 25 𝐼𝑏𝑚𝑜𝑙𝑒 → 𝐹 = 25 (46) = 1150 𝐼𝑏/ℎ𝑟

(Since no quantity of C2H5OH out from the process hence all quantity input are reacted)

Checking T.M.B. overall the process

𝐢𝐧𝐩𝐮𝐭 = 𝐅 = 𝟏𝟏𝟓𝟎 𝑰𝒃
𝐨𝐮𝐭𝐩𝐮𝐭 = 𝐏 + 𝑮 = 𝟏𝟏𝟎𝟎 + 𝟓𝟎 = 𝟏𝟏𝟓𝟎 𝑰𝒃
𝐶2 𝐻5 OH reacted
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑜𝑓 𝐶2 𝐻5 OH produced =
𝐶2 𝐻5 OH input to the reactor

80 1150 1150 − 920

= → 1150 = 0.8 (1150) + 0.8𝑅 → 𝑅 = = 287.5 𝐼𝑏/ℎ𝑟
100 1150 + 𝑅 0.8

Checking:
Ethanol input to the reactor = F + R = 1150 + 287.5 = 1437.5 Ib
Ethanol reacted = 1437.5(80/100) = 1150 Ib. = F
Ethanol un reacted = 1437.5 (20/100) = 287.5 Ib.=R

8
 Principles ch.12 Dr. Hameed R. Alamery

Example 4:
Methyl iodide is produced by adding HI to an excess amount of methanol according to the
following reaction:

𝐻𝐼 + 𝐶𝐻3 𝑂𝐻 → 𝐶𝐻3 𝐼 + 𝐻2 𝑂

𝑀𝑤𝑡. 128 32 142 18

Fresh HI are fed to process at a rate of 640 Ib / hr (F1). The degree of completion of the
reaction a 40 %. Calculate: the flow rates of streams (P), (W), (F2) and (R) shown in the
following block diagram.

(R) HI recycle

F1= 640 Ib/hr

HI P CH3I
Mixer Reactor Separator

W
F2 CH3OH 80 %CH3OH
20% H2O

Solution:
A// Basis: 1 hr. ≡ 640 Ib. of F1

1- Material balance overall the process

640
𝐻𝐼 𝑖𝑛𝑝𝑢𝑡 = = 5 Ib mole = HI reacted
128
(𝐒𝐢𝐧𝐜𝐞 𝐧𝐨 𝐪𝐮𝐚𝐧𝐭𝐢𝐭𝐲 𝐨𝐟 𝐇𝐈 𝐨𝐮𝐭 𝐟𝐫𝐨𝐦 𝐭𝐡𝐞 𝐩𝐫𝐨𝐜𝐞𝐬𝐬)
𝑪𝑯𝟑 𝐈 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 5 (142) = 710 𝐼𝑏/ℎ𝑟 = 𝑝

𝐼𝑏 20 90
𝑯𝟐 𝐎 𝑃𝑟𝑜𝑑𝑢𝑐𝑒𝑑 = 5 (18) = 90 = 𝑊( ) → 𝑊 = ( ) = 450 Ib/hr
ℎ𝑟 100 0.2
𝟖𝟎
𝑪𝑯𝟑 𝐎𝐇 𝐨𝐮𝐭𝐩𝐮𝐭 𝐢𝐧 𝐖 = 𝟒𝟓𝟎 ( ) = 𝟑𝟔𝟎 𝑰𝒃
𝟏𝟎𝟎

𝑪𝑯𝟑 𝐎𝐇 𝐢𝐧𝐩𝐮𝐭 = 𝑪𝑯𝟑 𝐎𝐇 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 + 𝑪𝑯𝟑 𝐎𝐇 𝐮𝐧𝐫𝐞𝐚𝐜𝐭𝐞𝐝

F2 = 5 (32) + 360 → 𝐹2 = 160 + 360 = 520 Ib/hr

9
 Principles ch.12 Dr. Hameed R. Alamery

Checking:
𝐢𝐧𝐩𝐮𝐭 = 𝐅𝟏 + 𝐅𝟐 = 𝟔𝟒𝟎 + 𝟓𝟐𝟎 = 𝟏𝟏𝟔𝟎 𝑰𝒃
𝐨𝐮𝐭𝐩𝐮𝐭 = 𝐏 + 𝑾 = 𝟕𝟏𝟎 + 𝟒𝟓𝟎 = 𝟏𝟏𝟔𝟎 𝑰𝒃

𝑚𝑎𝑥 16.25 𝑚𝑎𝑥 5

𝜉𝐶𝐻3 𝑂𝐻
= = 16.25 𝜉𝐻𝐼 = =5
1 1

Hence: HI is The Limiting reactant and CH3OH is the excess reactant.

𝐻𝐼 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝐝𝐞𝐠𝐫𝐞𝐞 𝐨𝐟 𝐜𝐨𝐦𝐩𝐨𝐥𝐞𝐭𝐢𝐨𝐧 =
𝐻𝐼 𝑖𝑛𝑝𝑢𝑡 𝑡𝑜 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑜𝑟

40 640
= → 𝟐𝟓𝟔 + 𝟎. 𝟒𝐑 = 𝟔𝟒𝟎 → 𝑹 = 𝟗𝟔𝟎 𝑰𝒃/𝒉𝒓
100 640 + 𝑅

Checking
𝐇𝐈 𝐢𝐧𝐩𝐮𝐭 𝐭𝐨 𝐭𝐡𝐞 𝐫𝐞𝐚𝐜𝐭𝐨𝐫 = 𝐅𝟏 + 𝐑 = 𝟔𝟒𝟎 + 𝟗𝟔𝟎 = 𝟏𝟔𝟎𝟎 𝑰𝒃
𝟒𝟎
𝐇𝐈 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝟏𝟔𝟎𝟎 ( ) = 𝟔𝟒𝟎 𝑰𝒃 = 𝑭𝟏
𝟏𝟎𝟎
𝟔𝟎
𝐇𝐈 𝐮𝐧𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝟏𝟔𝟎𝟎 ( ) = 𝟗𝟔𝟎 𝑰𝒃 = 𝑹
𝟏𝟎𝟎

10
 Principles ch.12 Dr. Hameed R. Alamery

Example 5:
Methanol can be produced according to the following reaction:

𝐶𝑂 + 2𝐻2 → 𝐶𝐻3 𝑂𝐻

𝑀𝑤𝑡. 28 2 32

A gaseous mixture (F) consists of 67.3 mol. % H2, 32.5 mol. % CO, and 0.2 mol. %CH4
are fed at a rate of 1000 Ib. mole/hr. to the process shown in the following block diagram.
Recycle (R)
67.3% H2 Divider
32.5% CO G x H2
0.2 % CH4 y CO
F= 1000 [Link] z CH4

Mixer Reactor Separator

P
100 %CH3OH

Since CH4 is not involve in the reaction, hence a purge stream (G) is used to maintain the
composition of CH4 in the recycle stream as 3.2 mol. %. If the conversion of CO =18%.
Calculate the flow rates of (P), (G), (R) and the composition of (R).

Solution:
Basis: 1 hr. ≡ 1000 Ibmole of F

Let x, y, z = mole fraction of H2, CO and CH4 in (R) & (G) respectively.

Note: that (R) and (G) have the same composition since the stream out from the
separator is separated to (R) & (G) by divider.

∴ 𝒁 = 𝟎. 𝟎𝟑𝟐

𝑪𝑯𝟒 𝐛𝐚𝐥𝐚𝐧𝐜𝐞 𝐨𝐯𝐞𝐫 𝐚𝐥𝐥 𝐩𝐫𝐨𝐜𝐞𝐬𝐬

0.2 2
1000 ( ) = 𝐺 (0.032) → 𝐺 = ( ) = 62.5 Ibmol./hr
100 0.032

𝑯𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝑯𝟐 𝐢𝐧𝐩𝐮𝐭 − 𝑯𝟐 𝐨𝐮𝐭𝐩𝐮𝐭

67.3
𝑯𝟐 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 1000 ( ) − 𝐺 (𝑋) = 673 − 62.5 𝑋 … … … … . . (1)
100

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 Principles ch.12 Dr. Hameed R. Alamery

𝐂𝐎 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 𝐂𝐎 𝐢𝐧𝐩𝐮𝐭 − 𝐂𝐎 𝐨𝐮𝐭𝐩𝐮𝐭

32.5
𝐂𝐎 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 1000 ( ) − 𝐺 (𝑦) = 325 − 62.5 𝑦 … … … … . . (2)
100

𝑺𝑖𝑛𝑐𝑒 𝐻2 reacted is 𝐭𝐰𝐢𝐜𝐞 𝐶𝑂 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 ℎ𝑒𝑛𝑐𝑒: Note: G & P≠ F

673 − 62.5 𝑋 = 2 ( 325 − 62.5 𝑦) = 650 − 125 𝑦 Why???

23 + 125𝑌
∴𝑋=( ) = 0.368 + 2 𝑦 … … … … . . (3)
62.5

𝒙+𝒚+𝒛 = 𝟏 → 𝒙 + 𝒚 = 𝟏 − 𝒛 = 𝟎. 𝟗𝟔𝟖 … … … … … … (𝟒)

0.968 − 0.368
Sub. 3 in (4) 0.368 + 2 𝑦 + 𝑦 = 0.968 → 𝑦= = 0.2
3
Sub. in 3 𝑋 = 0.368 + 2 (0.2) = 0.768

𝑪𝑯𝟑 𝐎𝐇 𝐏𝐫𝐨𝐝𝐮𝐜𝐞𝐝 = 𝐂𝐎 𝐫𝐞𝐚𝐜𝐭𝐞𝐝 = 325 − 62.5 𝑦 = 312.5 𝐼𝑏𝑚𝑜𝑙/ℎ𝑟 = (𝑃)

18 𝐶𝑂 reacted 312.5
𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑜𝑓 CO = = =
100 𝐶𝑂 input 0.2 𝑅 + 325

254
∴ 312.5 = 𝟎. 𝟎𝟑𝟔 𝐑 + 𝟓𝟖. 𝟓 → 𝑹 = = 7055.6 𝐼𝑏𝑚𝑜𝑙/ℎ𝑟
0.036

Composition of R
H2 x = 0.768 76.8 %
CO y = 0.20 20.0 %
CH4 Z= 0.032 3.2 %
Total 1 100 %

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 Principles ch.13 Dr. Hameed R. Alamery

Ideal and Real gases

Introduction:
This chapter deals with the pressure – volume –temperature (P-V-T) relationships for ideal
and real gaseous behavior of pure components and mixtures of gases.
These relation are of importance in all calculation involve gases such as energy balance,
combustion, thermodynamics and design of pressure vessels ……. Etc.

It is convenient to study relationships of gases by putting them in four separate sections:-

1. Ideal gas law.

2. Ideal gas mixtures.
3. Real gas relationships.
4. Real gas mixtures.

1- Ideal gas law

The ideal gas can be defined as that gas in which the average distance between the
molecules is great enough that the intermolecular forces are negligible, and the volume
of gas molecules is very small compared with the total volume of the gas and can be
neglected.
An ideal gas is an imaginary gas that obeys certain simple law known as “ideal gas law
“. The behavior of any real gas such as H2, O2, CO2 ….etc. approaches that of an ideal
gas at law pressure and high temperatures. Thus, the ideal gas law can be used for
simplicity in many engineering calculations at low pressure (up to 3 - 4 atm.) since it
gives incorrect result at higher pressures and lower temperatures.
 Ideal gas law was developed from the work of many scientist as follow:
A// Boyle law
Robert Boyle (1627 - 1691), an English chemist. In 1662 found that the volume of a certain
quantity of an ideal gas is inversely proportional to the absolute pressure at constant
temperature.
1
⃑ ⋉
Hence for one mole of an ideal gas, 𝑉 𝑃

⃑ = 𝐾1
𝑃𝑉 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇 … … … … … … . (1)

𝑽
𝑾𝒉𝒆𝒓𝒆 ⃑𝑽 = 𝒎𝒐𝒍𝒂𝒓 𝒗𝒐𝒍𝒖𝒎𝒆 = ; 𝑲𝟏 𝒊𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒏

1
 Principles ch.13 Dr. Hameed R. Alamery

Table 13.1: Pressure-Volume Data

Pressure (atm) Volume (mL) P×V=k (atm⋅mL)
0.5 1000 500
0.625 800 500
1.0 500 500
2.0 250 500
5.0 100 500
8.0 62.5 500
10.0 50 500

Figure 13.1: The pressure of a gas decreases as the volume increases, making Boyle's law
an inverse relationship.

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 Principles ch.13 Dr. Hameed R. Alamery

B// Charles and Gay-Lussac law

In 1787, they demonstrated that the volume of a certain quantity of an ideal gas varies
directly with absolute temperature at constant pressure.

⃑ ⋉ 𝑇
Hence for one mole of an ideal gas, 𝑉

⃑
𝑽
𝑖. 𝑒. ⃑ = 𝐾2 𝑇 𝑂𝑅
𝑉 = 𝑲𝟐 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃 … … … … … … . (2)
𝑻
𝑊ℎ𝑒𝑟𝑒 𝐾2 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

⃑⃑
P V
Combination of eq. 1 & 2 gives = R … … … … … … . (3)
T

𝑊ℎ𝑒𝑟𝑒 𝑅 𝑖𝑠 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Table 13.2: Temperature-Volume Data

⃑𝑽
Temperature (K) Volume (mL) = 𝑲
𝑻
50 20 0.40
100 40 0.40
150 60 0.40
200 80 0.40
300 120 0.40
500 200 0.40
1000 400 0.40

Figure 13.2: The volume of a gas increases as the Kelvin temperature increases.

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 Principles ch.13 Dr. Hameed R. Alamery

C// Avogadro Hypothesis

In 1811, Avogadro proposed his famous hypothesis that “equal volumes of different gases
contain the same number of molecules under the same condition of temperature and
⃑ ) of all gases of ideal behavior are equal at the
pressure. This means that molar volumes ( 𝑉
same temperature & pressure.

Thus, the constant (R) is the same for all gases. It is known “the universal gas constant”.

The ideal gas law usually put in the form:

𝑃 𝑉 = 𝑛 𝑅𝑇 … … … … … … . (4)
Where:
p = absolute pressure of the gas
V = total volume occupied by the gas
n = number of moles of the gas
R = ideal (universal) gas constant in appropriate units
T = absolute temperature of the gas

Several arbitrarily specified standard states (usually known as standard conditions, or S.C.
or S.T.P. for standard temperature and pressure) of temperature and pressure have specified
for gases by custom.

TABLE 13.3 Common Standard Conditions for the Ideal Gas

System T P ⃑
𝑽

SI 273.15 K 101.325 kPa 22.415 m3/kg mol

American 491.67 °R (32°F) 1 atm. ( 14.7 psia) 359.05 ft3 /lb mol
engineering

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 Principles ch.13 Dr. Hameed R. Alamery

EXAMPLE 13.1 Use of Standard Conditions to Calculate Volume from Mass

Calculate volume, in cubic meters, occupied by 40 kg of CO2 at standard conditions

assuming CO2 acts as an ideal gas.

Solution

Notice in this problem how the information that 22.42 m3, at S.C. =1 kg mol is applied to
transform a known number of moles into an equivalent number of cubic meters. An
alternate way to calculate the volume at standard conditions is to use, Equation (4).

EXAMPLE 13.2 Calculation of R Using the Standard Conditions

Find the value for universal constant R to match the following combination of units: For
1 g mol. of ideal gas when the pressure in atm. the volume is in cm3, and the temperature
is in K.

Solution

The following values are the ones to use (along with their units). At standard conditions:

5
 Principles ch.13 Dr. Hameed R. Alamery

The values of (R) in different units are as follow:

𝟑
𝟖𝟐. 𝟎𝟔 𝒂𝒕𝒎. 𝒄𝒎 ⁄𝒈 𝒎𝒐𝒍. 𝑲 𝑝𝑠𝑖𝑎. 𝑓𝑡 3⁄
10.73 𝐼𝑏 𝑚𝑜𝑙. °𝑅

𝟎. 𝟎𝟖𝟐𝟎𝟔 𝒂𝒕𝒎. 𝒍𝒊𝒕𝒆𝒓⁄𝒈 𝒎𝒐𝒍. 𝑲 𝑎𝑡𝑚. 𝑓𝑡 3⁄

0.73 𝐼𝑏 𝑚𝑜𝑙. °𝑅
𝑱⁄ 𝑓𝑡. 𝐼𝑏𝑓
𝟖. 𝟑𝟏𝟒 𝒎𝒐𝒍. 𝑲 1545 ⁄
𝐼𝑏 𝑚𝑜𝑙. °𝑅
𝟑
𝟖𝟑. 𝟏𝟒 𝒄𝒎 𝒃𝒂𝒓⁄𝒈 𝒎𝒐𝒍. 𝑲 𝑖𝑛 𝐻𝑔. 𝑓𝑡 3⁄
21.9 𝐼𝑏 𝑚𝑜𝑙. °𝑅

𝟏. 𝟗𝟖𝟕 𝒄𝒂𝒍⁄
𝒈 𝒎𝒐𝒍. 𝑲 1.987 𝐵𝑡𝑢 ⁄𝐼𝑏 𝑚𝑜𝑙. °𝑅

If a specific quantity of an ideal gas is changed from condition (1) to condition (2), then:

𝑃1 𝑉1 = 𝑛 𝑅𝑇1 … … … … … … . (5)

𝑃2 𝑉2 = 𝑛 𝑅𝑇2 … … … … … … . (6)
Hence,
𝑃1 𝑉1 𝑇1
( ) ( )= ( ) … … … … … … . (7)
𝑃2 𝑉2 𝑇2

 Volumetric & molar flow rate of ideal gas:

The relationship between volumetric flow rate and molar flow rate for ideal gas can
be derived from equation 4:

𝑉 𝑛
𝑃 ( ) = ( ) 𝑅𝑇
𝜃 𝜃

𝑅𝑇
i. e. Volumetric flow rate = molar flow rate ( ) … … … … (8)
𝑃

𝑉 𝑛 𝑅𝑇
( )= ( ) ( ) … … … … … … . . (8)
𝜃 𝜃 𝑃

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 Principles ch.13 Dr. Hameed R. Alamery

 Density & specific gravity of ideal gas:

Density of ideal gas can be estimated at any temperature and pressure from ideal gas
law:
𝑚𝑎𝑠𝑠
𝑃 𝑉 = 𝑛 𝑅𝑇 → 𝑃𝑉 = ( ) 𝑅𝑇
𝑀𝑤𝑡
𝑚𝑎𝑠𝑠 𝑃 𝑀𝑤𝑡
∴ 𝜌= = ( ) … … … … … … (9)
𝑉 𝑅𝑇

 The specific gravity (Spg) of a gas is estimated with reference to air either at
the same condition of the gas or at the standard condition (0 °C & 1 atm.).
 The spg of ideal gas compared to air at the same condition can be directly
estimated from ideal gas law:

𝑃 𝑀
( 𝑅 𝑇𝑤𝑡 )
𝜌𝑔𝑎𝑠 𝑔𝑎𝑠 𝑀𝑤𝑡𝑔𝑎𝑠
𝑆𝑝𝑔 = ( ) = = … … … (10)
𝜌𝑎𝑖𝑟 𝑃,𝑇 𝑃 𝑀𝑤𝑡
( 𝑅𝑇 ) 29
𝑎𝑖𝑟

Note: Eq. (10) is true for ideal gas only compared to air at the same P&T.

EXAMPLE 13.1

Find the numerical value of the universal gas constant (R) in the following units:
3 𝑓𝑡. 𝐼𝑏𝑓
(𝐴) 𝑎𝑡𝑚. 𝑓𝑡 ⁄𝐼𝑏 𝑚𝑜𝑙. 𝐾 (𝐵) 𝑱⁄𝒎𝒐𝒍. 𝑲 (𝐶) ⁄
𝐼𝑏 𝑚𝑜𝑙. °𝑅

Solution:-
(A) at S. C. P = 1 atm. , T = 273 K , ⃑⃑⃑𝑽 = 359 ft3 /lb mol

P ⃑V 1𝑎𝑡𝑚.× 359 ft3 /lb mol 𝑎𝑡𝑚. 𝑓𝑡3⁄

𝑅= = = 1.3145 𝐼𝑏 𝑚𝑜𝑙. 𝐾
T 273 𝑘

𝑁
(B) at S. C. P = 1 atm. = 101.3 kpa = 101300 , T = 273 K
𝑚2

𝑙𝑖𝑡𝑒𝑟 𝑚3 𝑚3
⃑⃑⃑𝑽 = 22.415 × = 0.022415
𝑚𝑜𝑙 1000 𝑙𝑖𝑡𝑒𝑟 𝑚𝑜𝑙

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 Principles ch.13 Dr. Hameed R. Alamery

𝑁 𝑚3
P ⃑V 101300 2 × 0.022415
𝑅= = 𝑚 𝑚𝑜𝑙
= 8.314 𝑱⁄𝒎𝒐𝒍. 𝑲
T 273 𝑘
𝐼𝑏𝑓 144 𝑖𝑛2 𝐼𝑏𝑓
(C) at S. C. P = 14.7 2
× 2
= 216.8 , T = 273 K
𝑖𝑛 𝑓𝑡 𝑓𝑡 2

𝐼𝑏𝑓
⃑
P V 216.8 × 359 ft3 /lb mol
𝑓𝑡2 𝑓𝑡. 𝐼𝑏𝑓
𝑅= = = 1545 ⁄𝐼𝑏 𝑚𝑜𝑙. °𝑅
T 492 °𝑅

EXAMPLE 13.2

60 gm of a paraffinic gas fills a 20 liters vessel at 32 °C and 22 psig. What is the

molecular formula of the gas? Given that:- R = 0.082 𝑎𝑡𝑚. 𝑙.⁄𝑔 𝑚𝑜𝑙. 𝐾

Solution:-
𝑇 = 32 + 273 = 305 𝑘
1 𝑎𝑡𝑚.
𝑃𝑎𝑏𝑠 = 𝑃𝑔𝑎𝑔𝑒 + 𝑃𝑎𝑡𝑚 = 22 + 14.7 = 36.7 𝑃𝑠𝑖𝑎 × = 2.5 𝑎𝑡𝑚
14.7 𝑃𝑠𝑖
𝑚𝑎𝑠𝑠
𝑃 𝑉 = 𝑛 𝑅𝑇 = ( ) 𝑅𝑇
𝑀𝑤𝑡
𝑎𝑡𝑚. 𝑙
𝑚𝑎𝑠𝑠 × 𝑅 × 𝑇 60 𝑔𝑚 × 0.082 𝑔 𝑚𝑜𝑙𝑒 𝑘 × 305 𝑘
∴ 𝑀𝑤𝑡 = =
𝑃𝑉 2.5 𝑎𝑡𝑚 × 20 𝑙
𝑔𝑚
= 30
𝑔 𝑚𝑜𝑙𝑒

The chemical formula of paraffinic is C nH2n+2

∴ 12(𝑛) + 1(2𝑛 + 2) = 30 → 14 𝑛 = 28 →
𝑛=2 𝑖. 𝑒. 𝑡ℎ𝑒 𝑔𝑎𝑠 𝑖𝑠 𝐶2 𝐻6 (𝒆𝒕𝒉𝒂𝒏𝒆)

8
 Principles ch.13 Dr. Hameed R. Alamery

Example 3:
Ten cubic feet of air at 70 F and 1.0 atm are heated to 600 F and compressed
to 2.50 atm. What is the volume occupied by the gas in state? It's final state?

Ans.
Since 𝑛1 = 𝑛2 (the number of moles of the gas does not change), and assumer ideal
gas (since law pressure), heater
𝑃1𝑉1 = 𝑛1𝑅 𝑇1 and 𝑃2𝑉2 = 𝑛2 𝑅 𝑇2
𝑇1 = 70 + 460 = 530 °𝑅 𝑇2 = 600 + 460 = 1060 °𝑅
𝑃1𝑉1 𝑃2 𝑉2 𝑃1 𝑉1 𝑇1
= → ( )( ) = … … . (𝐸𝑞. 7)
𝑇1 𝑇2 𝑃2 𝑉2 𝑇2
𝑉1 𝑃1𝑇2 10 𝑓𝑡 3 × 1𝑎𝑡𝑚 × 1060 °𝑅
𝑉2 = = = 8.0 𝑓𝑡 3
𝑃2 𝑇1 2.5𝑎𝑡𝑚 × 530 °𝑅
Example 4:
An: ideal paraffinic gas fills a 200 liters vessel at 25 ℃ 175 psig. The
specific gravity of the gas referred to air at the same conditions=2.0
What is the gas and it's mass in gm.?

Ans.
(𝑀 𝑤𝑡)𝑔𝑎𝑠
𝑆𝑃𝑔 = → (𝑀 𝑤𝑡)𝑔𝑎𝑠 = 2 (29) = 58
29
56
12𝑛 = 1(2𝑛 + 2) = 58 → 𝑛 = = 4 𝑇ℎ𝑒 𝑔𝑎𝑠 𝑖𝑠 𝐶4𝐻10 𝑏𝑢𝑡𝑎𝑛𝑒
14
𝑃𝑉 = 𝑛𝑅𝑇
1 𝑎𝑡𝑚
P = 17.5 + 14.7 = 32.2 psia × = 2.19 atm
14.7
T = 273 + 25 = 298k
𝑝𝑣 2.19 𝑎𝑡𝑚 (200 𝑙𝑖𝑡𝑒𝑟𝑠)
n= = = 17.91 𝑚𝑜𝑙.
𝑅𝑇 0.08206 (𝑎𝑡𝑚. 𝑙) ⁄ (𝑔𝑚. 𝑚𝑜𝑙𝑒. 𝑘 ) (298𝑘)
∴ 𝑀𝑎𝑠𝑠 = 𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒 × 𝑀𝑤𝑡. = 17.91 × 58 = 1039 𝑔𝑚

9
 Principles ch.13 Dr. Hameed R. Alamery

2- Ideal Gas Mixtures:

In gaseous mixture each component contributes its share to word the pressure and volume
of the mixture which is proportional to its mole fraction in the mixture.
Two basic terms are widely used in calculation of gaseous mixtures:
 Partial pressure (ᵱ)
It is the pressure exerted by each component of a gaseous mixture if it occupies alone the
total volume of the mixture at the same temperature.

 Partial Volume (v)

It is the volume occupied by each component of a gaseous mixture if it exists alone under
the total pressure of the mixture at the same temperature.
 Daltons law of Partial pressures:
This law states that the total pressure of ideal gas mixture is equal to the same of partial
pressures of component.
𝑃 = 𝑝𝐴 + 𝑝𝐵 + 𝑝𝐶 + ⋯ … … … … … . 𝑒𝑡𝑐.
𝑖. 𝑒.
𝑛

𝑃 = ∑ 𝑝𝑖 … … … … . … … … (11)
𝑖=1
Where:-
P: total pressure of the mixture.
p: partial pressure of component (i).
The relationship between (P) & (pi) can be derived from ideal gas law:

Let N: total number of moles of mixture.

𝑛𝐴 𝑛𝐵 𝑛𝐶 : moles of component A, B, C respectivily.
V: total volume of the mixture.
∴ 𝑁 = 𝑛𝐴 + 𝑛𝐵 + 𝑛𝐶
𝐹𝑜𝑟 𝑔𝑎𝑠 𝑚𝑖𝑥𝑡𝑢𝑟𝑒: 𝑃 𝑉 = 𝑁 𝑅𝑇 … … … … … … . (∗)

𝐹𝑜𝑟 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴: 𝑃𝐴 𝑉 = 𝑛𝐴 𝑅𝑇 … … … … … … . (𝑎)

𝐹𝑜𝑟 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐵: 𝑃𝐵 𝑉 = 𝑛𝐵 𝑅 𝑇 … … … … … … . (𝑏)
𝐹𝑜𝑟 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐶: 𝑃𝐶 𝑉 = 𝑛𝐶 𝑅 𝑇 … … … … … … . (𝑐)
Divide each of equation (a), (b), (c) by equation (*) gives:
10
 Principles ch.13 Dr. Hameed R. Alamery

𝑝𝐴 𝑉 𝑛𝐴 𝑅 𝑇 𝑝𝐴 𝑛𝐴
( )=( ) → ( )=( ) = 𝑦𝐴 𝑖. 𝑒. 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴
𝑃𝑉 𝑁𝑅𝑇 𝑃 𝑁
∴ 𝒑𝑨 = 𝐏 𝒚 𝑨
𝑰𝒏 𝒈𝒆𝒏𝒆𝒓𝒂𝒍 𝒑𝒊 = 𝐏 𝒚𝒊 … … … … … … . . (𝟏𝟐)

That is the partial pressure of any component in an ideal gas mixture is equal to the mole
fraction of that component times the total pressure.
 Amagat’s law of Partial volumes:
This law states that the total volume of ideal gas mixture is equal to the sum of partial
volumes of component.
𝑉 = 𝑣𝐴 + 𝑣𝐵 + 𝑣𝐶 + ⋯ … … … … … . 𝑒𝑡𝑐.
𝑖. 𝑒.
𝑛

𝑉 = ∑ 𝑣𝑖 … … … … . … … … (13)
𝑖=1
Where:-
𝑉: total volume of the mixture
𝑣𝑖 ∶ partial volume of component (i).
The relationship between (V) & (vi) can be derived from ideal gas law:
Let P: total Pressure of the mixture.

∴ 𝐹𝑜𝑟 𝑔𝑎𝑠 𝑚𝑖𝑥𝑡𝑢𝑟𝑒: 𝑃 𝑉 = 𝑁 𝑅𝑇 … … … … … … . (∗)

𝐹𝑜𝑟 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴: 𝑃 𝑣𝐴 = 𝑛𝐴 𝑅𝑇 … … … … … … . (𝑎)

𝐹𝑜𝑟 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐵: 𝑃 𝑣𝐵 = 𝑛𝐵 𝑅 𝑇 … … … … … … . (𝑏)
𝐹𝑜𝑟 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐶: 𝑃 𝑣𝐶 = 𝑛𝐶 𝑅 𝑇 … … … … … … . (𝑐)
Divide each of equation (a), (b), (c) by equation (*) gives:
𝑃 𝑣𝐴 𝑛𝐴 𝑅 𝑇 𝑣𝐴 𝑛𝐴
( )=( ) → ( )=( )
𝑃𝑉 𝑁𝑅𝑇 𝑉 𝑁
= 𝑦𝐴 𝑖. 𝑒. 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝐴

∴ 𝒗𝑨 = 𝐕 𝒚𝑨
𝑰𝒏 𝒈𝒆𝒏𝒆𝒓𝒂𝒍 𝒗𝒊 = 𝐕 𝒚 𝒊 … … … … … … . . (𝟏𝟒)

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 Principles ch.13 Dr. Hameed R. Alamery

That is the partial volume of any component in an ideal gaseous mixture is equal to the
mole fraction of that component times the total volume.
𝑣𝑖
∴ ( ) = 𝑦𝑖
𝑉
𝐅𝐨𝐫 𝐢𝐝𝐞𝐚𝐥 𝐠𝐚𝐬, 𝐯𝐨𝐥𝐮𝐦𝐞 𝐟𝐫𝐚𝐜𝐭𝐢𝐨𝐧 = 𝐦𝐨𝐥𝐞 𝐟𝐫𝐚𝐜𝐭𝐢𝐨𝐧
EXAMPLE 13.5

A tank containing a quantity of nitrogen at 100 °F, 1.6 Ib of CH4 are added. So that the
partial pressure of N2= 48 psia and that of CH4=12 psia. If the temperature remains
constant at 100 °F and if it is assumed ideal behavior of gases.

Calculate A// Composition of the mixture, B// mass of nitrogen originally presented in the
tank, C// volume of the tank, and D// partial volumes of N2 and CH4.

Solution:

A//
𝑛

𝑃 = ∑ 𝑝𝑖 = 48 + 12 = 60 𝑝𝑠𝑖𝑎
𝑖=1

𝑝𝑁2 48 𝑝𝐶𝐻4 12
𝑦𝑁2 = ( )= = 0.8 ; 𝑦𝐶𝐻4 = ( )= = 0.2
𝑃𝑡𝑜𝑡 60 𝑃𝑡𝑜𝑡 60
The mixture consists of 80 mol % N2 & 20 mol% CH4

B//
𝑚𝑎𝑠𝑠 1.6
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒 𝐶𝐻4 = = ( ) = 𝑜. 1 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑀𝑤𝑡 16
100 80
∴ 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 0.1 ( ) = 𝑜. 5 𝐼𝑏 𝑚𝑜𝑙𝑒 → ∴ 𝑚𝑜𝑙 𝑁2 = 0.5 ( )=
20 100
0.4 𝐼𝑏 𝑚𝑜𝑙𝑒
∴ 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁2 = 0.4( 28) = 11.2 Ib
C//
𝑝𝑠𝑖𝑎. 𝑓𝑡 3
0.5 𝐼𝑏 𝑚𝑜𝑙𝑒 × 10.73
∴ 𝑉𝑡𝑜𝑡 =
𝑛𝑅𝑇
= 𝐼𝑏 𝑚𝑜𝑙𝑒 °𝑅 × 560 °𝑅 = 50 𝑓𝑡 3
𝑃𝑡𝑜𝑡 60 𝑝𝑠𝑖𝑎

∴ 𝑣𝑁2 = 𝑉𝑡𝑜𝑡 𝑦𝑁2 = 50 (0.8) = 40 𝑓𝑡 3

∴ 𝑣𝐶𝐻4 = 𝑉𝑡𝑜𝑡 𝑦𝐶𝐻4 = 50 (0.2) = 10 𝑓𝑡 3

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 Principles ch.13 Dr. Hameed R. Alamery

EXAMPLE 13.6

A tank containing 0.15 Ib mole of nitrogen at 100 °F & 20 Psia. A quantity of hot paraffinic
gas are added to the tank. The partial pressure of N2 after mixing=21 psia, and that of of the
paraffinic gas=14 psia. The specific gravity of the mixture refined to air at the same
conditions= 0.8. Assuming ideal behavior of gases.
Calculate (a) Volume of the tank, (b)Ib moles of the paraffinic gas added, (c) Final
temperature of the mixture and (d) Identify the paraffinic gas.
Ans

( 𝒂) 𝑭𝒐𝒓 𝑵𝟐 𝒏𝒍𝒚 𝒃𝒆𝒇𝒐𝒓𝒆 𝒂𝒅𝒅𝒊𝒕𝒊𝒐𝒏 𝒐𝒇 𝒕𝒉𝒆 𝒑𝒂𝒓𝒂𝒇𝒇𝒊𝒏𝒊𝒄 𝒈𝒂𝒔 = 𝑷𝑽 = 𝒏 𝑹𝑻

𝒏𝑹𝑻
𝑽= = = 𝟒𝟓 𝒇𝒕𝟑
𝑷 𝟐𝟎 𝒑𝒔𝒊𝒂

(𝒃) 𝒑𝒕𝒐𝒕 = 𝚺𝒑𝒊 = 𝟐𝟏 + 𝟏𝟒 = 𝟑𝟓 𝒑𝒔𝒊𝒂

𝒑𝑵𝟐 𝟐𝟏 𝒏 𝟎.𝟏𝟓 𝟎.𝟏𝟓
𝒚𝑵𝟐 = = 𝟑𝟓 = 𝟎. 𝟔 ; 𝒚𝑪𝑯𝟒 = 𝒏 𝑵𝟐 = 𝒏 𝒕𝒐𝒕. = 𝟎. 𝟔 𝒏𝒕𝒐𝒕. = = 𝟎. 𝟐𝟓 𝑰𝒃 𝒎𝒐𝒍𝒆
𝒑𝒕𝒐𝒕 𝒕𝒐𝒕 𝟎.𝟔

𝟎.𝟏
∴ 𝐦𝐨𝐥𝐞 𝐨𝐟 𝐩𝐚𝐫𝐚𝐟𝐟𝐢𝐧𝐢𝐜 𝐠𝐚𝐬 = 𝟎. 𝟐𝟓 − 𝟎. 𝟏𝟓 = 𝟎. 𝟏 𝐈𝐛 𝐦𝐨𝐥𝐞 → 𝒚𝒑 = 𝟎.𝟐𝟓 = 𝟎. 𝟒

𝑷𝑽 𝟑𝟓 (𝟒𝟓)
( 𝒄) 𝑻 = = = 𝟓𝟐𝟕 °𝐑 = 𝟏𝟐𝟕℉ 𝐅𝐢𝐧𝐚𝐥 𝐭𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞 𝐨𝐟 𝐦𝐢𝐱𝐭𝐮𝐫𝐞
𝒏𝑹 𝟎.𝟐𝟓 (𝟏𝟎.𝟕𝟑)

𝑴𝒎𝒊𝒙
(𝒅) 𝑺𝒑𝒈 = = 𝟎. 𝟖 → 𝑴𝒎𝒊𝒙 𝟐𝟗 (𝟎. 𝟖) = 𝟐𝟑. 𝟐
𝟐𝟗

23.2 = 𝑀𝑁2 𝑦𝑁2 + 𝑀𝑃 𝑦𝑃 = 28 (𝑜. 6) + 𝑀𝑃 (0.4)

23.2 − 16.8 6.4
𝑀𝑃 = = = 16
0.4 0.4

∴ 𝐶𝑛 𝐻2𝑛+2 12(𝑛) + 1(2𝑛 + 2) = 16 → 𝑛 = 1

; 𝑖. 𝑒 𝑡ℎ𝑒 𝑔𝑎𝑠 𝑖𝑠 𝑚𝑒𝑡ℎ𝑎𝑛𝑒 (𝐶𝐻4)

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 Principles ch.13 Dr. Hameed R. Alamery

Example7:
Two similar tanks connected by a valve which is initially closed. The first tank contains 0.1
Ib. mole of 𝑁2 at 30psia and 100℉. The second tank contains 𝐶𝑂2 at 220℉. When the valve
connecting the tanks is opened and the gases are completely mixed, it is found that the partial
pressure of 𝑁2 = 16.8psia and that of 𝐶𝑂2 = 25.2 psia. Assuming ideal gaseous behavior,
calculate: (a) volume of each tank in (𝑓𝑡 3 ), (b) Ib. mole of 𝐶𝑂2 in the second tank, (c) the
reading of the pressure gauge of the second tank before opening the valve, (d) the final
temperature in (℉) of the mixture after opening the valve, and (e) the partial volume of 𝑁2
and 𝐶𝑂2 .

Ans.
𝑛𝑁2 𝑅𝑇 0.1 (10.73)(560)
(𝑎) 𝑉1 = = = 20 𝑓𝑡 3 = 𝑉2 (since the tanks are similar)
𝑃 30

(b) 𝑃𝑡𝑜𝑡 = Σ𝑝𝑖 =16.8+25.2 = 42psia

𝑃𝑁2
𝑦𝑁2 = = 0.4 𝐼𝑏. 𝑚𝑜𝑙𝑒
𝑃𝑡𝑜𝑡
𝑛𝑁2 0.1
𝑦𝑁2 = ⟹ 𝑛𝑡𝑜𝑡 = = 0.25 Ib. mole
𝑛𝑡𝑜𝑡 0,4

𝑛𝐶𝑂2 = 0.25 − 0.1 = 0.15 𝐼𝑏. 𝑚𝑜𝑙𝑒

𝑛𝐶𝑂2 0.15
𝑦𝐶𝑂2 = = =0.6
𝑛𝑡𝑜𝑡 0,25

𝑛𝑐𝑜2 0,15 (10.73)(680)

(c) For 2 not tank before mixing p= = = 54.7psia
𝑉 20

𝑝𝑔𝑎𝑛𝑔 = 𝑝𝑎𝑏𝑠 − 𝑝𝑎𝑡𝑚 = 54.7 – 14.7 = 40 psig the reading of pressure gauge.
(d) After opening the valve, 𝑣𝑡𝑜𝑡 =𝑣1 + 𝑣2 =40 𝑓𝑡 3
𝑝𝑡𝑜𝑡 𝑣𝑡𝑜𝑡 42(40)
T= = = 626.3 °𝑅 ⟹ T=166.3 ℉
𝑛𝑡𝑜𝑡 𝑅 (0.25)(10.73)

(e) 𝑣𝑁2 = 𝑣𝑡𝑜𝑡 𝑦𝑁2 = 40(0.4) = 16 𝑓𝑡 3

𝑣𝐶𝑂2 = 𝑣𝑡𝑜𝑡 𝑦𝐶𝑂2 = 40(0.6) = 24 𝑓𝑡 3

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 Principles ch.13 Dr. Hameed R. Alamery

 Critical state and critical constants:

It is the state at which no distinction between liquid and vapour and the specific properties
such as density, viscosity, heat capacity…etc. of the gas and liquid phases of the substance
become identical. At this point there is only one phase neither liquid nor gaseous but it is
known as critical state. The critical state of any substance is described by three constant
quantities known as “critical constants”. These constants are defined as follow:
A// Critical Temperature (Tc)
It is the highest temperature at which liquid and vapour of a pure materials can exist in
equilibrium. Any gas cannot be liquefied under any applied pressure unless it is cooled
below its critical temperature.
B// Critical pressure (Pc)
It is the highest pressure at which liquid and vapour of a pure material can exist in
equilibrium.

C// Critical volume (⃑⃑⃑⃑𝑽𝑐)

It is the volume occupied by one mole of the substance at the critical [Link] is expressed
either in cm3 /gm mole or in ft3/ Ib mole

Values of Tc, Pc, and ⃑⃑⃑⃑𝑽𝑐 for various substances are shown in the following Tables.
Critical constants are commonly used in relationships of real gas and many other
thermodynamic concepts and calculations.
Reduced Conditions and reduced parameters
These are conditions of the gas expressed mathematically in terms of its, Critical conditions
by three dimensionless quantities. These quantities are:
𝑇
(a) Reduced temperature 𝑇𝑟 = For H2 and He only
𝑇𝐶
𝑇
𝑃 𝑇𝑟 = 𝑇𝐶 +8 𝑘
(b) Reduced pressure 𝑃𝑟 =
𝑃𝐶
𝑃
𝑃𝑟 =
⃑⃑⃑𝑽 𝑃𝐶 + 8 𝑎𝑡𝑚
(c)Reduced volume ⃑⃑⃑𝑽𝑟 =
⃑⃑⃑𝑽𝐶

Some of real gas relationships involve reduced parameters rather than critical constant of
the gas.

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Principles ch.13 Dr. Hameed R. Alamery

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Principles ch.13 Dr. Hameed R. Alamery

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 Principles ch.13 Dr. Hameed R. Alamery

(3) Real Gas Relationships

Most gases can be assumed to Act as ideal
gases at room Temperature and pressure.
The difference between the actual value
of P ⃑⃑⃑𝑉 and that calculated Rom ideal gas law
at any temperature clearly increases with
increasing pressure as shown in the
following figure.
Thus, real gas relations must be used rather
than ideal gas low to compute P-V-T values
of a gas at higher pressures (more than 3-
4atm.)

Two mathematical methods are commonly used for prediction real gas properties:

(a) Equations of State:

These are empirical relations involve two or more coefficients which relate pressure .volume
.and temperature of and temperature of a pure real gas (or mixtures).These equations were
proposed to fit a large mass of experimental data and also to permit accurate interpolation
between experimental data points. The following table lists a few of the commonly used
equations of state from among the hundreds that have been proposed.
Only one of these equations (van der waal’s equation) is used in computational problems in
this stage of study since it is the simplest and most well a known than others. However,
applications at of other equations of state in computational problems are involved in the
contents of thermodynamics -2nd year.
They provide a continuous function to facilitate calculation of physical properties based on
differentiation and integration of p-V-T relationships. Finally, they provide a point of
departure for the treatment of the properties of mixtures.
Some of the advantages of using an equation of state versus other prediction methods are:
1. Values of p-V-T can be predicted with reasonable error in regions where no data exist.
2. Only a few values of coefficients are needed in the equation to be able to predict gas
properties versus collecting large amounts of data by experiment.
3. The equations can be manipulated on a computer whereas graphics methods cannot.

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 Principles ch.13 Dr. Hameed R. Alamery

Some disadvantages are:

1. The form of an equation is hard to change to fit new data.
2. Inconsistencies may exist between equations for p-V-T and equations for other
physical properties.
3. Usually the equation is quite complicated and may not be easy to solve for p. VI or T
because of its nonlinearity
If you plan to use a specific equation of state such as one of those listed in Table 15.1, you
have numerous choices, no one of which win consistently give the best results.
 Van der Waals Equations:
In this equation, the effect of the attractive forces among the molecules, and also the effect
of the volume accupied by the molecules them seleves were taken into account and
𝑛2 𝑎
included in the ideal gas law by adding the term( ) to the pressure and subtracting the
𝑉2
term (n b) from the volume. Thus, the equation was put in the following forms:

𝑛2 𝑎
(𝑃 + ) (𝑉 − 𝑛 𝑏 ) = 𝑛 𝑅 𝑇 … … … … … … … . . (15)
𝑉2

OR
𝑅𝑇 𝑎
𝑃=( )− ( ) … … … … … … (16)
⃑⃑⃑𝑽 − 𝑏 ⃑⃑⃑𝑽2
Where (a) and (b) are van der waals constants which can be estimated from the critical
constant according to the following relationships:
27 𝑅2 𝑇𝑐 2 𝑅 𝑇𝐶
𝑎=( ) ;;;;;;;;;;; 𝑏= ( ) … … … … … … (17)
64 𝑃𝐶 8 𝑃𝐶

𝑎𝑡𝑚 𝑓𝑡 3
If Tc is taken in (K) and Pc in (atm), then 𝑅 = 1.3145 (𝐼𝑏 𝑚𝑜𝑙𝑒 𝐾 ) . The value of (a) & (b)
for most substances are listed in the preceding table.

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Principles ch.13 Dr. Hameed R. Alamery

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 Principles ch.13 Dr. Hameed R. Alamery

B// Law of corresponding states or (Compressibility Factor Method):

This law states that “all gases have the same reduced volume at the same reduced
temperature & pressure and have similar deviation from ideal gas law”.
A convenient way of expressing this deviation is by introducing a dimensionless factor
(Z) known as “compressibility factor” to the ideal gas law:

𝑃𝑉 =𝑍𝑛𝑅𝑇 … … … … … … … . . (18)
Hence the compressibility factor (Z) accounts for non-ideal behavior. The deviation of (Z)
from unity is an indication to the degree of non-ideality of the gas since Z=1 for ideal gas.
The compressibility factor is function of the reduced temperature and pressure of the gas

𝑖. 𝑒. 𝑍 = 𝑓 (𝑃𝑟 , 𝑇𝑟 ) … … … … … … … . . (19)
The compressibility factor (Z) is commonly & easily estimated graphically from a”
generalized compressibility chart “from (𝑃𝑟 & 𝑇𝑟 ). this chart was constructed
assuming 𝑍𝐶 = 0.27.

Where (ZC) is the compressibility factor at the critical point. It is defined as:
𝑃𝐶 ⃑⃑⃑𝑽𝐶
𝑍𝐶 = ( ) … … … … … … . (20)
R 𝑇𝐶

It is important to note that ZC for most substances are ranged between 0.23 to 0.30, and
more than 60 % of substances have Z C between 0.26 – 0.28 with average value of 0.27.
The accuracy of this method depends on the deviation of ZC of the substance from this
value (0.27). However, another parameter termed as “acentric factor (Ꞷ)” can be included
for more accurate estimation of (Z) but calculation becomes heavy. The generalized chart
yields quite reasonable value for engineering purposes.
Some references add another helpful parameter to the generalized compressibility chart.
This parameter is “the ideal reduced volume” (𝑉𝑟 𝑖 ) which is defined as:
⃑⃑⃑𝑽
𝑉𝑟 𝑖 =
⃑⃑⃑𝑽𝐶 𝑖
𝑅 𝑇𝐶
Where: (⃑⃑⃑𝑽𝐶 𝑖 ) is ideal critical volume, i.e. ⃑⃑⃑𝑽𝐶 𝑖 =
P𝐶

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Principles ch.13 Dr. Hameed R. Alamery

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 Principles ch.13 Dr. Hameed R. Alamery

4- Real Gas Mixtures:

The same relationships and for pure real gas can be used for real gaseous mixtures
with special techniques for calculating the coefficients involved in these equation.
A// Van der waals Equation:
This equation can be used for real gas mixtures. Van der waals constants of the mixture (a
mix. & b mix) are estimated from those of pure components as follow:

1⁄ 1⁄ 1⁄ 1⁄
2
𝑎𝑚𝑖𝑥 = 𝑎𝐴 2 𝑦𝐴 + 𝑎𝐵 2 𝑦𝐵 + 𝑎𝐶 2 𝑦𝐶 + ⋯

And ……… (21)

𝑏𝑚𝑖𝑥 = 𝑏𝐴 𝑦𝐴 + 𝑏𝐵 𝑦𝐵 + 𝑏𝐶 𝑦𝐶 + ⋯
Then,
𝑛2 𝑎𝑚𝑖𝑥
(𝑃 + ) (𝑉 − 𝑛 𝑏𝑚𝑖𝑥 ) = 𝑛 𝑅 𝑇 … … … … … … … . . (22)
𝑉2

B// Compressibility Factor Method:

This method can be used for ideal gas mixture so that:
𝑃 𝑉 = 𝑍𝑚 𝑛 𝑅 𝑇 … … … … … … … . . (23)
Where Zm is the mean “Compressibility Factor for the mixture”
Methods were proposed for estimation Zm (Dalton’s, Amagat’s and Kay’s methods).
However, kay’s method is both simple and reasonably accurate than others. It is based
an estimation Zm from the “pseudocritical constant of mixture” (𝑃𝑐𝑚 & 𝑇𝑐𝑚 ).

Where:
𝑃𝐶𝑚 = 𝑃𝐶𝐴 𝑦𝐴 + 𝑃𝐶𝐵 𝑦𝐵 + 𝑃𝐶𝐶 𝑦𝐶 + ⋯ … … … … … …. (24)

And
𝑇𝐶𝑚 = 𝑇𝐶𝐴 𝑦𝐴 + 𝑇𝐶𝐵 𝑦𝐵 + 𝑇𝐶𝐶 𝑦𝐶 + ⋯ … … … … … …. (25)
The reduced parameter for the mixture can be estimated from (𝑃𝑐𝑚 & 𝑇𝑐𝑚 ):
𝑃 𝑇
𝑃𝑟𝑚 = & 𝑇𝑟𝑚 = … … … … … … … . (26)
𝑃𝐶𝑚 𝑇𝐶𝑚
Then
𝑖. 𝑒. 𝑍𝑚 = 𝑓 (𝑃𝑟𝑚 , 𝑇𝑟𝑚 ) … … … … … … … . . (27)

23
 Principles ch.13 Dr. Hameed R. Alamery

Example 11:
A pressure vessel with volume of 131 ft 3 contains ethane (C2H6) at 360 psia and 90 °F.
Calculate the mass in pounds of ethane in this vessel.
Solution:
Since, ethane present under very high pressure, hence it is considered as real gas.
Calculation according to the compressibility factor method are follow.
From table 𝑃𝐶 = 48.8 𝑎𝑡𝑚. 𝑇𝐶 = 305.2 𝑘 𝐺𝑖𝑣𝑒𝑛 𝑜𝑟 𝑔𝑒𝑡 𝑓𝑟𝑜𝑚 𝑡𝑎𝑏𝑙𝑒
1𝑘
𝑇 = 90 + 460 = 550 °𝑅 (1.8 𝑅) = 305.5 𝑘

𝑃 360 𝑃𝑠𝑖 𝑎𝑡𝑚. 𝑇 305.5

𝑃𝑟 = = × = 0.5 & 𝑇𝑟 = = = 1.0 Z= 0.8 from chart
𝑃𝐶 48.8 𝑎𝑡𝑚. 14.7 𝑝𝑠𝑖 𝑇𝐶 305.2

𝑃𝑉 360 𝑝𝑠𝑖𝑎 ( 131 𝑓𝑡 3 )

𝑛=( )= = 10 𝐼𝑏 𝑚𝑜𝑙𝑒
ZRT 𝑝𝑠𝑖𝑎 𝑓𝑡 3
0.8 ( 10.73 ) (550 °𝑅)
𝐼𝑏 𝑚𝑜𝑙 °𝑅
∴ 𝑚𝑎𝑠𝑠 = 𝑛 × 𝑀𝑤𝑡 = 10 (30) = 300 𝐼𝑏
Example 12:
A pressure vessel with volume of 131 ft 3 contains 300 Ib of ethane (C2H6) at 90 °F.
Calculate the pressure in psia by Vander waals equation. Given that Mwt of C2H6 =30

Solution: From table 𝑃𝐶 = 48.8 𝑎𝑡𝑚. 𝑇𝐶 = 305.2 𝑘 𝐺𝑖𝑣𝑒𝑛 𝑜𝑟 𝑔𝑒𝑡 𝑓𝑟𝑜𝑚 𝑡𝑎𝑏𝑙𝑒
27 𝑅2 𝑇𝑐 2 27 (1.3145)2 (305.5)2 𝑓𝑡 3
𝑎=( ) = = 1391 𝑎𝑡𝑚( )2
64 𝑃𝐶 64 (48.8) 𝐼𝑏 𝑚𝑜𝑙𝑒

𝑎𝑡𝑚. 𝑓𝑡 3
𝑅 𝑇𝐶 1.3145 𝐼𝑏 𝑚𝑜𝑙𝑒 𝑘 (305.5 𝑘)
𝑏= ( ) = = 1.028
8 𝑃𝐶 8 (48.8 𝑎𝑡𝑚. )
𝑛2 𝑎
(𝑃 + 2 ) (𝑉 − 𝑛 𝑏) = 𝑛 𝑅 𝑇
𝑉

102 (1391) 𝑎𝑡𝑚. 𝑓𝑡 3

(𝑃 + ) ( 131 − 10 (1.028) ) = 10 𝐼𝑏 𝑚𝑜𝑙𝑒 (0.73 ) (550 °𝑅)
1312 𝐼𝑏 𝑚𝑜𝑙𝑒 °𝑅
(𝑃 + 8.106) (131 − 10.28 ) = 4015 →→ 120.72 𝑃 = 3036.4
𝟏𝟒. 𝟕 𝒑𝒔𝒊
𝑷 = 𝟐𝟓. 𝟏𝟓 𝒂𝒕𝒎 ( ) = 𝟑𝟕𝟎 𝒑𝒔𝒊𝒂
𝟏 𝒂𝒕𝒎.
24
 Principles ch.13 Dr. Hameed R. Alamery

Example 13:
66 Ib of propane are contained in vessel with volume of 11 ft 3 at 170 °C. Calculate the
pressure in the vessel using compressibility factor method.
Solution: Method (1)
𝑚𝑎𝑠𝑠 66
𝑛= = = 1.5 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑀𝑤𝑡 44
𝑇 = 170 + 273 = 443 𝑘
For propane 𝑃𝐶 = 42 𝑎𝑡𝑚. 𝑇𝐶 = 369.9 𝑘 𝐺𝑖𝑣𝑒𝑛 𝑜𝑟 𝑔𝑒𝑡 𝑓𝑟𝑜𝑚 𝑡𝑎𝑏𝑙𝑒
𝑃 𝑃 𝑇 443
𝑃𝑟 = = & 𝑇𝑟 = = = 1.2
𝑃𝐶 42 𝑇𝐶 369.9
Solve by trial & error
P assume Pr Z 𝑍 𝑛𝑅𝑇
𝑃𝐶𝑎𝑙𝑐. = ( )
V
42 1.0 0.8 0.8 (1.5)(1.1345)(443)
𝑃𝐶𝑎𝑙𝑐. = = 63.5
11
55 1.3 0.73 58
56.5 1.35 0.72 57.2
56.8 P = 56.8

Solution: Method (2)

𝑈𝑠𝑒 𝑖𝑑𝑒𝑎𝑙 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑣𝑜𝑙𝑢𝑚𝑒 (⃑⃑⃑𝑽𝑟 𝑖 )

𝑓𝑡 3
⃑⃑⃑𝑽 = 𝑉 = 11
= 7.33
𝑛 1.5 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑅 𝑇𝐶 ( 1.3145)(369.9) 𝑓𝑡 3
⃑⃑⃑𝑽𝐶 𝑖 = = = 11.58
P𝐶 42 𝐼𝑏 𝑚𝑜𝑙𝑒
⃑⃑⃑𝑽 7.33
⃑⃑⃑𝑽𝑟 𝑖 = = = 0.63
⃑⃑⃑𝑽𝐶 𝑖 11.58
𝑃
𝐹𝑟𝑜𝑚 𝑖𝑛𝑡𝑒𝑟𝑠𝑒𝑐𝑡𝑖𝑜𝑛 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 (⃑⃑⃑𝑽𝑟 𝑖 ) & 𝑇𝑟 𝑤𝑒 𝑔𝑒𝑡 𝑃𝑟 = 1.3 = 𝑃 𝑓𝑟𝑜𝑚 𝑓𝑖𝑔. (𝐹)
𝐶

∴ 𝑃 = 1.3 (𝑃𝐶 ) = 1.3 (42) = 54.6 𝑎𝑡𝑚.

25
 Principles ch.13 Dr. Hameed R. Alamery

Example 14:
3.5 kg of oxygen are contained in tank of 27.8 liter under 70 atm. What is the
temperature?
Solution:
𝐹𝑟𝑜𝑚 𝑡𝑎𝑏𝑙𝑒 𝑃𝐶 = 49.7 𝑎𝑡𝑚. 𝑇𝐶 = 154.3 𝑘 𝐺𝑖𝑣𝑒𝑛 𝑜𝑟 𝑔𝑒𝑡 𝑓𝑟𝑜𝑚 𝑡𝑎𝑏𝑙𝑒
𝑚𝑎𝑠𝑠 3.5
𝑛= = = 0.109 𝑘𝑔 𝑚𝑜𝑙𝑒
𝑀𝑤𝑡 32
𝑉 27.8 𝑙𝑖𝑡𝑒𝑟 𝑚3 𝑚3
⃑⃑⃑𝑽 = = × = 0.255
𝑛 0.109 𝑘𝑔 𝑚𝑜𝑙 1000 𝑙𝑖𝑡𝑒𝑟 𝑘𝑔 𝑚𝑜𝑙𝑒
Method (1)
𝑅 𝑇𝐶 ( 0.08206) (154.3 𝑘) 𝑚3
⃑⃑⃑𝑽𝐶 𝑖 = = = 0.255
P𝐶 49.7 𝑘𝑔 𝑚𝑜𝑙𝑒
⃑⃑⃑𝑽 0.255 𝑃 70
⃑⃑⃑𝑽𝑟 𝑖 = = = 1.0 → 𝑃𝑟 = = = 1.4
⃑⃑⃑𝑽𝐶 𝑖 0.255 𝑃𝐶 49.7
𝑇
𝐹𝑟𝑜𝑚 𝑖𝑛𝑡𝑒𝑟𝑠𝑒𝑐𝑡𝑖𝑜𝑛 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 (⃑⃑⃑𝑽𝑟 𝑖 ) & 𝑃𝑟 𝑤𝑒 𝑔𝑒𝑡 𝑇𝑟 = 1.6 = 𝑇 𝑓𝑟𝑜𝑚 𝑓𝑖𝑔. (𝐹)
𝐶

∴ 𝑇 = (𝑇𝑟 ) × (𝑇𝐶 ) = 1.6 (154.3) = 247 𝐾 = −26 ℃

OR it can be solved by trial & error as in example13

27 𝑅2 𝑇𝑐 2 27 (0.08206)2 (154.3)2 𝑚3
𝐹𝑜𝑟 𝑂𝑥𝑦𝑔𝑒𝑛 𝑎 = ( ) = = 1.361 𝑎𝑡𝑚( )2
64 𝑃𝐶 64 (49.7) 𝑘𝑔 𝑚𝑜𝑙𝑒

𝑎𝑡𝑚. 𝑚3
0.08206
𝑅 𝑇𝐶 𝑘𝑔 𝑚𝑜𝑙𝑒 𝑘 (154.3 𝑘) 𝑚3
𝑏= ( ) = = 0.0318
8 𝑃𝐶 8 (49.7 𝑎𝑡𝑚. ) 𝑘𝑔 𝑚𝑜𝑙𝑒
𝑛2 𝑎
(𝑃 + ) (𝑉 − 𝑛 𝑏 ) = 𝑛 𝑅 𝑇
𝑉2

(0.109)2 (1361)
(70 + ) (0.0278 − 0.109 (0.0318) ) = 0.109 (0.08206) 𝑇
( 0.0278)2

90.92 × 0.0243
(70 + 20.92) (0.0243 ) = 0.00394 𝑇 →→ 𝑇 = = 247 𝐾 = −26℃
0.00884

26
 Principles ch.13 Dr. Hameed R. Alamery

Example 15:
Fifty pounds of propane (C3H8) are contained in cylinder at 223 °F under 665 psig.
Calculate the volume of the cylinder use Van der waals equation.
Solution:
𝑎𝑡𝑚.
𝑃 = 665 + 14.7 = 679.7 𝑝𝑠𝑖𝑎 × = 46.2 𝑎𝑡𝑚. →→ 𝑇 = 223 + 460 = 683°𝑅
14.7 𝑝𝑠𝑖𝑎
𝑓𝑡 3 𝑓𝑡 3
𝐹𝑜𝑟𝑚 𝑡𝑎𝑏𝑙𝑒 𝑎 = 2374 𝑎𝑡𝑚( )2 ; 𝑏 = 1.446
𝐼𝑏 𝑚𝑜𝑙𝑒 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑚𝑎𝑠𝑠 50
𝑛= = = 1.136 𝐼𝑏 𝑚𝑜𝑙𝑒
𝑀𝑤𝑡 44
𝑛2 𝑎
(𝑃 + ) (𝑉 − 𝑛 𝑏 ) = 𝑛 𝑅 𝑇
𝑉2

(1.136)2 (2374)
(46.2 + ) (𝑉 − 1.136 (1.446) ) = 1.136 (0.73) ( 683)
( 𝑉)2
(3064)
(46.2 + ) (𝑉 − 1.643 ) = 566.4
𝑉2
(3064) 5034
46.2 𝑉 + − 75.9 − 2 − 566.4 = 0
𝑉 𝑉
46.2 𝑉 3 − 642.3 𝑉 2 + 3064 𝑉 − 5034 = 0 𝑀𝑖𝑙𝑡𝑝𝑙𝑦 𝑉 2
𝑉 3 − 13.9 𝑉 2 + 66.3 𝑉 − 109 = 0 𝑑𝑖𝑣𝑖𝑑𝑒 𝑏𝑦 46.2
𝑇ℎ𝑖𝑠 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑐𝑎𝑛 𝑏𝑒 𝑠𝑜𝑙𝑣𝑒𝑑 𝑏𝑦 Newton’s method according to the 𝑓𝑜𝑙𝑙𝑜𝑤𝑖𝑛𝑓 𝑒𝑞𝑢.
𝒇 (𝑽𝒏 )
𝑽𝒏+𝟏 = 𝑽𝒏 −
𝒇− (𝑽𝒏 )
𝑊ℎ𝑒𝑟𝑒 𝑓(𝑉 ) = 𝑉 3 − 13.9 𝑉 2 + 66.3 𝑉 − 109 … … … . (1)
𝑎𝑛𝑑 𝑓 − (𝑉 ) = 3𝑉 2 − 27.8 𝑉 + 66.3 … … … . (2)
𝑛𝑅𝑇
𝑉0 𝑎𝑠 𝑡ℎ𝑒 𝑓𝑖𝑟𝑠𝑡 𝑡𝑟𝑖𝑎𝑙 𝑐𝑎𝑛 𝑏𝑒 𝑒𝑠𝑡𝑖𝑚𝑎𝑡𝑒𝑑 𝑓𝑟𝑜𝑚 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑙𝑎𝑤 𝑉0 =
𝑃
𝑛𝑅𝑇 1.136 × 0.73 × 683
𝑉0 = = = 12.26 𝑓𝑡 3
𝑃 46.2
𝐹𝑟𝑜𝑚 𝑒𝑞𝑢. (1) 𝑓(𝑉0 ) = (12.26)3 − 13.9 (12.26)2 + 66.3 (12.26) − 109 = 457.3
𝑓 − (𝑉0 ) = 3(12.26)2 − 27.8 (12.26) + 66.3 = 176

27
Principles ch.13 Dr. Hameed R. Alamery

𝒇 (𝑽𝟎 ) 𝟒𝟓𝟕. 𝟑
𝑽𝟏 = 𝑽𝟎 − = 𝟏𝟐. 𝟐𝟔 − = 𝟏𝟐. 𝟐𝟔 − 𝟐. 𝟓𝟗 = 𝟗. 𝟔𝟕 𝒇𝒕𝟑
𝒇− (𝑽𝟎 ) 𝟏𝟕𝟔. 𝟒

𝒇𝒐𝒓 𝒏𝒆𝒙𝒕 𝒕𝒓𝒊𝒂𝒍 𝑽𝟏 = 𝟗. 𝟔𝟕 , 𝒇 (𝑽𝟏 ) = 𝟏𝟑𝟔. 𝟑 , 𝒇− (𝑽𝟏 ) = 𝟕𝟖 ⟹ 𝑽𝟐 = 𝟕. 𝟗𝟐 𝒇𝒕𝟑

𝑺𝒊𝒎𝒊𝒍𝒂𝒓𝒚 𝑽𝟑 , 𝑽𝟒 . . … … . 𝒂𝒓𝒆 𝒄𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒆𝒅 𝒕𝒊𝒍𝒍 𝒕𝒉𝒆 𝒇𝒊𝒏𝒂𝒍 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 (𝑽𝒏 ) = 𝟓 𝒇𝒕𝟑
𝐶ℎ𝑒𝑐𝑘 𝑓 (𝑉5 ) = (5)3 − 13.9 (5)2 + 66.3 (5) − 109 = ⋯ … … …
= 125 − 347.5 + 331.5 − 109 = 0

𝑯𝒆𝒏𝒄𝒆 𝑽𝒏 = 𝑽𝒏−𝟏

28
 Principles ch.13 Dr. Hameed R. Alamery

Example 16:
A gaseous mixture consists of 20 mol % CH4 and 80 mol % C2H4 at 735 psia and 70 °C.
Calculate the molar volume in ft 3/Ib mole by
(𝐴)ideal gas law , , (B)kay’s method , , (C)Van der waal’s equation
Solution:
A// ideal gas law.
𝑇 = 70 + 273 = 343 𝑘 𝑜𝑟 𝑇 = 70 (1.8) + 32 = 158 ℉ = 618 °𝑅
𝑛 𝑅 𝑇 ( 1) × (10.73) × (618)
∴ 𝑉= = = 9.0 𝑓𝑡 3
𝑃 735

B// kay’s method.

Solve by kay’s method.
Component Tc, k Pc, y y Tc y Pc
atm
CH4 191.1 45.8 0.2 38.2 9.2

C2H4 282.8 50.7 0.8 226.2 40.6

𝑻𝒄𝒎 = 264.4 𝑷𝒄𝒎 = 𝟒𝟗. 𝟖

𝑃 735 𝑇 343
𝑃𝑟 = = = 1.0 & 𝑇𝑟 = = = 1.3
𝑃𝐶𝑚 49.8 × 14.7 𝑇𝐶𝑚 264.4

𝐹𝑟𝑜𝑚 𝑐ℎ𝑎𝑟𝑡 𝑍𝑚 = 0.85

𝑍𝑚 𝑛 𝑅 𝑇
∴ 𝑉= = (0.85) × (9) = 7.65 𝑓𝑡 3
𝑃

C// Van der waals Method:

1⁄
2 1⁄ 1⁄ 𝑓𝑡 3 2
𝑎𝑚𝑖𝑥 = 0.2 (581.2) 2 + 0.8 (1150) 2 = 31.95 → 𝑎𝑚𝑖𝑥 = 1021 𝑎𝑡𝑚 ( )
𝐼𝑏 𝑚𝑜𝑙
And
𝑓𝑡 3
𝑏𝑚𝑖𝑥 = 0.2 (0.6855) + 0.8 (0.9165) = 0.870
𝐼𝑏 𝑚𝑜𝑙
Then use Newton’s method to calculate (V) as in example 15
𝑓 (𝑉 ) = 𝑉 3 + 9.9 𝑉 2 + 20.4 𝑉 = 0 → 𝑉 = 7.5 𝑓𝑡 3

29
 Principles ch.13 Dr. Hameed R. Alamery

Ideal and Real gases

Introduction:
This chapter deals with the pressure – volume –temperature (P-V-T) relationships for ideal
and real gaseous behavior of pure components and mixtures of gases.
These relation are of importance in all calculation involve gases such as energy balance,
combustion, thermodynamics and design of pressure vessels ……. Etc.

It is convenient to study relationships of gases by putting them in four separate sections:-

1. Ideal gas law.

2. Ideal gas mixtures.
3. Real gas relationships.
4. Real gas mixtures.

1- Ideal gas law

The ideal gas can be defined as that gas in which the average distance between the
molecules is great enough that the intermolecular forces are negligible, and the
volume of gas molecules is very small compared with the total volume of the gas and
can be neglected.
An ideal gas is an imaginary gas that obeys certain simple law known as “ideal gas
law “. The behavior of any real gas such as H2, O2, CO2 ….etc. approaches that of an
ideal gas at law pressure and high temperatures. Thus, the ideal gas law can be used
for simplicity in many engineering calculations at low pressure (up to 3 - 4 atm.)
since it gives incorrect result at higher pressures and lower temperatures.
 Ideal gas law was developed from the work of many scientist as follow:
A// Boyle law
Robert Boyle (1627 - 1691), an English chemist. In 1662 found that the volume of
a certain quantity of an ideal gas is inversely proportional to the absolute pressure at
constant temperature.
1
⃑ ⋉
Hence for one mole of an ideal gas, 𝑉 𝑃

⃑ = 𝐾1
𝑃𝑉 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇 … … … … … … . (1)

𝑽
𝑾𝒉𝒆𝒓𝒆 ⃑𝑽 = 𝒎𝒐𝒍𝒂𝒓 𝒗𝒐𝒍𝒖𝒎𝒆 = ; 𝑲𝟏 𝒊𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝒏

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 Principles ch.13 Dr. Hameed R. Alamery

Table 13.1: Pressure-Volume Data

Pressure (atm) Volume (mL) P×V=k (atm⋅mL)
0.5 1000 500
0.625 800 500
1.0 500 500
2.0 250 500
5.0 100 500
8.0 62.5 500
10.0 50 500

Figure 13.1: The pressure of a gas decreases as the volume increases, making Boyle's law
an inverse relationship.

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 Principles ch.13 Dr. Hameed R. Alamery

B// Charles and Gay-Lussac law

In 1787, they demonstrated that the volume of a certain quantity of an ideal gas varies
directly with absolute temperature at constant pressure.

⃑ ⋉ 𝑇
Hence for one mole of an ideal gas, 𝑉

⃑
𝑽
𝑖. 𝑒. ⃑ = 𝐾2 𝑇 𝑂𝑅
𝑉 = 𝑲𝟐 𝑎𝑡 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑃 … … … … … … . (2)
𝑻
𝑊ℎ𝑒𝑟𝑒 𝐾2 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

⃑⃑
P V
Combination of eq. 1 & 2 gives = R … … … … … … . (3)
T

𝑊ℎ𝑒𝑟𝑒 𝑅 𝑖𝑠 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Table 13.2: Temperature-Volume Data

⃑𝑽
Temperature (K) Volume (mL) = 𝑲
𝑻
50 20 0.40
100 40 0.40
150 60 0.40
200 80 0.40
300 120 0.40
500 200 0.40
1000 400 0.40

Figure 13.2: The volume of a gas increases as the Kelvin temperature increases.

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 Principles ch.13 Dr. Hameed R. Alamery

C// Avogadro Hypothesis

In 1811, Avogadro proposed his famous hypothesis that “equal volumes of different gases
contain the same number of molecules under the same condition of temperature and
⃑ ) of all gases of ideal behavior are equal at the
pressure. This means that molar volumes ( 𝑉
same temperature & pressure.

Thus, the constant (R) is the same for all gases. It is known “the universal gas constant”.

The ideal gas law usually put in the form:

𝑃 𝑉 = 𝑛 𝑅𝑇 … … … … … … . (4)
Where:
p = absolute pressure of the gas
V = total volume occupied by the gas
n = number of moles of the gas
R = ideal (universal) gas constant in appropriate units
T = absolute temperature of the gas

Several arbitrarily specified standard states (usually known as standard conditions, or S.C.
or S.T.P. for standard temperature and pressure) of temperature and pressure have specified
for gases by custom.

TABLE 13.3 Common Standard Conditions for the Ideal Gas

System T P ⃑
𝑽

SI 273.15 K 101.325 kPa 22.415 m3/kg mol

American 491.67 °R (32°F) 1 atm. ( 14.7 psia) 359.05 ft3 /lb mol
engineering

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 Principles ch.13 Dr. Hameed R. Alamery

EXAMPLE 13.1 Use of Standard Conditions to Calculate Volume from Mass

Calculate volume, in cubic meters, occupied by 40 kg of CO2 at standard conditions

assuming CO2 acts as an ideal gas.

Solution

Notice in this problem how the information that 22.42 m3, at S.C. =1 kg mol is applied to
transform a known number of moles into an equivalent number of cubic meters. An
alternate way to calculate the volume at standard conditions is to use, Equation (4).

EXAMPLE 13.2 Calculation of R Using the Standard Conditions

Find the value for universal constant R to match the following combination of units: For
1 g mol. of ideal gas when the pressure in atm. the volume is in cm3, and the temperature
is in K.

Solution

The following values are the ones to use (along with their units). At standard conditions:

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 Principles ch.13 Dr. Hameed R. Alamery

The values of (R) in different units are as follow:

𝟑
𝟖𝟐. 𝟎𝟔 𝒂𝒕𝒎. 𝒄𝒎 ⁄𝒈 𝒎𝒐𝒍. 𝑲 𝑝𝑠𝑖𝑎. 𝑓𝑡 3⁄
10.73 𝐼𝑏 𝑚𝑜𝑙. °𝑅

𝟎. 𝟎𝟖𝟐𝟎𝟔 𝒂𝒕𝒎. 𝒍𝒊𝒕𝒆𝒓⁄𝒈 𝒎𝒐𝒍. 𝑲 𝑎𝑡𝑚. 𝑓𝑡 3⁄

0.73 𝐼𝑏 𝑚𝑜𝑙. °𝑅
𝑱⁄ 𝑓𝑡. 𝐼𝑏𝑓
𝟖. 𝟑𝟏𝟒 𝒎𝒐𝒍. 𝑲 1545 ⁄
𝐼𝑏 𝑚𝑜𝑙. °𝑅
𝟑
𝟖𝟑. 𝟏𝟒 𝒄𝒎 𝒃𝒂𝒓⁄𝒈 𝒎𝒐𝒍. 𝑲 𝑖𝑛 𝐻𝑔. 𝑓𝑡 3⁄
21.9 𝐼𝑏 𝑚𝑜𝑙. °𝑅

𝟏. 𝟗𝟖𝟕 𝒄𝒂𝒍⁄
𝒈 𝒎𝒐𝒍. 𝑲 1.987 𝐵𝑡𝑢 ⁄𝐼𝑏 𝑚𝑜𝑙. °𝑅

If a specific quantity of an ideal gas is changed from condition (1) to condition (2), then:

𝑃1 𝑉1 = 𝑛 𝑅𝑇1 … … … … … … . (5)

𝑃2 𝑉2 = 𝑛 𝑅𝑇2 … … … … … … . (6)
Hence,
𝑃1 𝑉1 𝑇1
( ) ( )= ( ) … … … … … … . (7)
𝑃2 𝑉2 𝑇2

 Volumetric & molar flow rate of ideal gas:

The relationship between volumetric flow rate and molar flow rate for ideal gas can
be derived from equation 4:

𝑉 𝑛
𝑃 ( ) = ( ) 𝑅𝑇
𝜃 𝜃

𝑅𝑇
i. e. Volumetric flow rate = molar flow rate ( ) … … … … (8)
𝑃

𝑉 𝑛 𝑅𝑇
( )= ( ) ( ) … … … … … … . . (8)
𝜃 𝜃 𝑃

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 Principles ch.13 Dr. Hameed R. Alamery

 Density & specific gravity of ideal gas:

Density of ideal gas can be estimated at any temperature and pressure from ideal gas
law:
𝑚𝑎𝑠𝑠
𝑃 𝑉 = 𝑛 𝑅𝑇 → 𝑃𝑉 = ( ) 𝑅𝑇
𝑀𝑤𝑡
𝑚𝑎𝑠𝑠 𝑃 𝑀𝑤𝑡
∴ 𝜌= = ( ) … … … … … … (9)
𝑉 𝑅𝑇

 The specific gravity (Spg) of a gas is estimated with reference to air either at
the same condition of the gas or at the standard condition (0 °C & 1 atm.).
 The spg of ideal gas compared to air at the same condition can be directly
estimated from ideal gas law:

𝑃 𝑀
( 𝑅 𝑇𝑤𝑡 )
𝜌𝑔𝑎𝑠 𝑔𝑎𝑠 𝑀𝑤𝑡𝑔𝑎𝑠
𝑆𝑝𝑔 = ( ) = = … … … (10)
𝜌𝑎𝑖𝑟 𝑃,𝑇 𝑃 𝑀𝑤𝑡
( 𝑅𝑇 ) 29
𝑎𝑖𝑟

Note: Eq. (10) is true for ideal gas only compared to air at the same P&T.

EXAMPLE 13.4

60 gm of a paraffinic gas fills a 20 liters vessel at 32 °C and 22 psig. What is the

molecular formula of the gas? Given that:- R = 0.082 𝑎𝑡𝑚. 𝑙.⁄𝑔 𝑚𝑜𝑙. 𝐾

Solution:-
𝑇 = 32 + 273 = 305 𝑘
1 𝑎𝑡𝑚.
𝑃𝑎𝑏𝑠 = 𝑃𝑔𝑎𝑔𝑒 + 𝑃𝑎𝑡𝑚 = 22 + 14.7 = 36.7 𝑃𝑠𝑖𝑎 × = 2.5 𝑎𝑡𝑚
14.7 𝑃𝑠𝑖
𝑚𝑎𝑠𝑠
𝑃 𝑉 = 𝑛 𝑅𝑇 = ( ) 𝑅𝑇
𝑀𝑤𝑡
𝑎𝑡𝑚. 𝑙
𝑚𝑎𝑠𝑠 × 𝑅 × 𝑇 60 𝑔𝑚 × 0.082 𝑔 𝑚𝑜𝑙𝑒 𝑘 × 305 𝑘
∴ 𝑀𝑤𝑡 = =
𝑃𝑉 2.5 𝑎𝑡𝑚 × 20 𝑙
𝑔𝑚
= 30
𝑔 𝑚𝑜𝑙𝑒

The chemical formula of paraffinic is C nH2n+2

∴ 12(𝑛) + 1(2𝑛 + 2) = 30 → 14 𝑛 = 28 →
𝑛=2 𝑖. 𝑒. 𝑡ℎ𝑒 𝑔𝑎𝑠 𝑖𝑠 𝐶2 𝐻6 (𝒆𝒕𝒉𝒂𝒏𝒆)