Billion: The British say that a billion is a million million

(1,000,000,000,000). American say that a billion is a thousand million

(1,000,000,000) and insist that a million million is actually a trillion. The
Canadian Press agrees with the Americans

http://www.scit.wlv.ac.uk/~jphb/american.html

Please note that "tonne" is not a British spelling of "ton" but a quite separate
metric unit equal to 1000 kg as distinct from the British ton of 2240 lbs (=
1016.96 kg).

Billion: thousand million The old British usage in which a billion was a
million2 is now largely obsolete and most British speakers would assume
the American meaning. Careful users avoid the words altogether and use
exponent notation. The usage continued
trillion = tri+(m)illion = million3 = 1018
quadrillion = quad+(m)illion = million4 = 1024
centillion = cent+(m)illion = million100 = 10600
CHBI 201 1
The American naming seems to work on the principle 103+(number3)
 CHAPTER 4
MATERIAL BALANCES

CHBI 201 2
 CONSERVATION OF MASS
Mass is neither created nor destroyed
9
3 5
Reactor
10
11
1
Distillation 4
2
12 13

6 Heat 8
Seperator
Exchanger

14
7

{Input} + {Genn} - {Consumption} {Output} = {Accumulation}

CHBI 201 3
 SYSTEMS
Systems
OPEN or CLOSED
Any arbitrary portion of or a whole process that you
want to consider for analysis
Reactor, the cell, mitochondria, human body, section of a
pipe
Closed System
Material neither enters nor leaves the system
Changes can take place inside the system
Open System
Material can enter through the boundaries

CHBI 201 4
 STEADY-STATE
Steady-State
Nothing is changing with time
@ steady-state accumulation = 0

500 kg 100 kg/min

100 kg/min
H2O H2O H2O

Rate of addition = Rate of removal

Unsteady-State (transient system)

{Input} {Output}

CHBI 201 5
 PROCESSES
Batch Process
Feed is fed at the beginning of the process

Continuous Process
The input and outputs flow continuously throughout the
duration of proces

Semibatch Process
Any process neither batch nor continuous

CHBI 201 6
 Balances on Continuous Steady-state
Processes
Input + Generation = Output + Consumption
If the balance is on a nonreactive species, the generation and
consumption will be 0.
Thus, Input = Output
Example
Input of 1000 kg/h of benzene+toluene containing 50% B by mass is separated
by distillation column into two fractions.
B: the mass flow rate of top stream=450 kg/h
T: the mass flow rate of bottom stream=475 kg/h
m1 kg Toluene/h
450 kg Benzene/h
1000 kg /h
Benzene + Toluene Distillation
%50 Benzene by
mass 475 kg Toluene/h
CHBI 201 7
M2 kg Benzene/h
Balances on Continuous Steady-state
Processes
Solution of the example Input = Output
Benzene balance

.
1000 kg/h 0.5 = 450 kg/h + m2
.
m2 = 50 kg/h Benzene

Toluene balance
.
1000
. kg/h 0.5 = 475 kg/h + m1
m1 = 25 kg/h Toluene
CHBI 201 8
BALANCES ON BATCH PROCESSES
Initial Input + Generation = Final Output + Consumption
Objective: generate as many independent equations as the
number of unknowns in the problem

D F=B+D
F.xF = D.xD + B.xB
F
(W+A)
F.yF = D.yD + B.xB
x: mole fraction of W
B
y: mole fraction of A

CHBI 201 9
EXAMPLE (Batch Process)
Centrifuges are used to seperate particles in the range of 0.1 to 100 m
in diameter from a liquid using centrifugal force. Yeast cells are
recovered from a broth ( a mix with cells) using tubular centrifuge.
Determine the amount of the cell-free discharge per hour if 1000 L/hr is
fed to the centrifuge, the feed contains 500 mg cells/L, and the product
stream contains 50 wt% cells. Assume that the feed has a density of 1
g/cm3.

Feed (broth) 1000 L/hr Concantrated cells P(g/hr)

Centrifuge
500 mg cells/L feed 50 % by weight cells

( d= 1 g/cm3)
Cell-free discahrge D(g/hr)

CHBI 201 10
 EXAMPLE (Batch Process)
Centrifuges are used to seperate particles in the range of 0.1 to 100 m in diameter
from a liquid using centrifugal force. Yeast cells are recovered from a broth ( a mix
with cells) using tubular centrifuge. Determine the amount of the cell-free
discharge per hour if 1000 L/hr is fed to the centrifuge, the feed contains 500 mg
cells/L, and the product stream contains 50 wt% cells. Assume that the feed has a
density of 1 g/cm3.

Feed (broth) 1000 L/hr Concantrated cells P(g/hr)

Centrifuge
500 mg cells/L feed 50 % by weight cells

(d= 1 g/cm3)
Cell-free discharge D(g/hr)
Cell balance
500 mg cells 1g 0.5 g cells
1000 L feed . . . P[g/hr]
1 L feed 1000 mg 1gP
P 1000 g/hr
Fluid balance L 1g 10cm 3 1dm 3 6 g
1000 ( ) 10
Input: (106 500) g/h fluid h cm3 1dm L h
Output 1: 1000g/h . 0.5 = 500 g/h fluid
CHBI Output
201 2: D(g/h) = (106 500)g/h 500 g/h = (106 -103)g/h11fluid
 FLOW CHARTS
Boxes and other symbols are used to represent process
units.
Write the values and units of all known streams
Assign algebraic symbols to unknown stream variables

100 mol C3H8

Combustion 50 mol C3H8
Condenser
Chamber
750 mol O2
1000 mol O2
3760 mol N2
3760 mol N2
150 mol CO2
200 mol H2O
CHBI 201 12
EXAMPLE (Flow charts)
Humidification and Oxygenation Process in the Body: An exp. on
the growth rate of certain organisms requires an environemnt of
humid air enriched in oxygen. Three input streams are fed into an
evaporator to produce an output stream with the desired composition.
A: liquid water, fed at a rate of 20 cm3/min, B: Air, C: Pure oxygen
(with a molar flow rate one-fifth of the molar flow rate of stream B)

n.3 mol/min
0.2 n.1 mol O2/min
0.015 mol H2O/mol
C
y mol O2/mol
(0.985 y ) mol N2/mol
n.1 mol air/min B A

0.21 mol O2/mol 20 cm3 H2O /min

0.79 mol N2/mol n.2 mol H2O/min

CHBI 201 13
 EXAMPLE (Flow chart)
n2 = 20 cm3 H2O/min . 1 g H2O/cm3 . 1 mol/18.02 g
n2 = 1.11 mol H2O/min
H2O Balance
n2 mol H2O/min = n3 mol/min . 0.015 mol H2O/mol
n3 = 74.1 mol/min
Total Mole Balance
0.2 n1 + n1 + n2 = n3
n1 = 60.8 mol/min
N2 Balance
n1 mol/min . 0.79 mol N2/mol = n3 mol/min . (0.985-y) mol N2/mol
y = 0.337 mol O2/mol
CHBI 201 14
 FLOWCHART SCALING

n1
n3
A
n2

Scale factor: 100 100 n1

100 n3
A
100 n2

CHBI 201 15
DEGREE OF FREEDOM ANALYSIS (df)
ndf = nunknowns nindep.eqns

If ndf = 0
Problem can be solved (determined)
If ndf > 0
Unknowns > knowns (underspecified)
If ndf < 0
overspecified (no solution)

Material balances,
Energy balances,
Process specificaitons,
Physical props&laws,
CHBI 201
Physical constraints 16
 EXAMPLE 1
Example H20 is given
Humid air Condenser Dry air
(n4) O2 In the
(n0) O2
(n5) N2 condenser,
(n1) N2 95% of H2O
(n6) H2O
in the inlet
(n2) H2O
air is
(n3) H2O condensed.
225 L/h

7 unknowns (n0 -> n6) 7 equations needed

3 independent material balance
n3 = .V
n0/n1 = 21/79
n3 = 0.95 n2

One more equation is needed

Volume is not conserved!
CHBI 201 Use consistent units (mole, kg) 17
EXAMPLE 2
A continuous mixer mixes NaOH with H2O to produce
an aqueous solution of NaOH. Determine the
composition and flow rate of the product, if the flow
rate of NaOH is 1000 kg/hr and the ratio of the flow
rate of H2O to the product solution is 0.9.

System boundary
Nsp = number of species
Ns = number of streams
Nu = total number of variables
H2O NaOH
M

Product
CHBI 201 18
EXAMPLE 2 - continue
Streams FEED WATER PRODUCT

Species
NaOH FNaOH WNaOH PNaOH Nu = 3(2+1) = 9
H2O FH2O WH2O PH2O
Total F W P Last row in the table

Specifications: ratio of two streams

the % conversion in a reaction
the value of each concentration, flow
rate, T, P, , V, etc.
a variable is not present in a stream,
hence ,it is 0
CHBI 201 19
EXAMPLE 3
A cylinder containing CH4, C2H6, and N2 has to be prepared containing a
CH4 to C2H6 mole ratio of 1.5 to 1. Avaliable to prepare the mixture are
1) a cylinder containing a mixture of 80% N2 and 20% CH4
2) a cylinder containing a mixture of 90% N2 and 10% C2H6
3) a cylinder containing a mixture of pure N2
What is the number of degrees of freedom?

CHBI 201 20
 EXAMPLE 3 - continue

F4
F1
CH4 xCH4
CH4 0.2 F3
N2 xN2
N2 0.8 N2 1
C2H6 xC2H6

F2
C2H6 0.1
N2 0.9

Unknowns: 3 xi and 4 Fi

CHBI 201 21
 EXAMPLE 3 - continue

Equations:
Material balance (CH4, C2H6, N2)
One specified ratio xCH /xC H = 1.5
4 2 6

One summation of mole fractions x 1 for F

i 4
5 independent equations

Ndf = 7 5 = 2

If you pick a basis as F4=1, one other value has to

be specified in order to solve the problem.
CHBI 201 22
 Balances on Multiple-unit Processes
40 kg/hr 30 kg/hr

0.9 kg A/kg 0.6 kg A/kg

0.1 kg B/kg 0.4 kg B/kg

Q1 Q2
1 3
x1 x2 Q3
100 kg/hr 2
x3
0.5 kg A/kg
0.5 kg B/kg 30 kg/hr 4

0.3 kg A/kg
0.7 kg B/kg
CHBI 201 23
Balances on Multiple-unit Processes
Q : mass flow rate
You should treat any
xA : mass fraction of A
junction as a process unit!
1-xA : mass fraction of B
Number of unknowns = 6
Number of equations = 2+2+2 = 6
Therefore, solution exists

100 = 40 + Q1 Q1 = 60 kg/hr
1
100.(0.5) = 40.(0.9) + 60.(x1) x1 = 0.233

2
30 + Q1 = Q2 Q2 = 90 kg/hr
x2 = 0.256

30 + Q3 = Q2 Q3 = 60 kg/hr 3
CHBI 201 x3 = 0.083 24
CHBI 201 25
 RECYCLE & BYPASS STREAM
It is rare that a chemical reaction A B proceeds to
completion in a reactor. Its efficiency is never 100. Some A
in the product !
To find a way to send the A back to feed you need a
seperation and recycle equipment, this would decrease the
cost of purchasing more A.
If a fraction of the feed to a process unit is diverted
around the unit and combined with the output stream, this
process is called bypass.
Feed Product Feed Process
rxn Sep. Unit

Recycle Bypass stream

CHBI 201 26
 EXAMPLE (pg 110)

Feed: Fresh air with 4 mole% H2O(v) is cooled and dehumidified to a

water content of 1.7 mole% H2O.
Fresh air is combined with a recycle stream of dehumidified air.
The blended stream entering unit contains 2.3 mole% H2O. In the air
conditioner some of the water is removed as liquid.
Take 100 mole of dehumidified air delivered to the room, calculate
moles of feed, water condensed, dehumidified air recycled.

CHBI 201 27
 EXAMPLE - continue

n5 (mol) 0.983 DA, 0.017 W

n1 (mol)
AIR n4 (mol) 100 mol
0.04 W CONDITIONER 0.983 DA
0.017 W
0.96 DA 0.017 W(v)
0.983 DA

n3 mole W()
n2 (mol)
0.977 DA
CHBI 201 28
0.023 W(v)
 EXAMPLE - continue
Overall system: 2 variables (n1, n3)
2 balance equations (two species)
Degree of freedom = 0
(n1, n3) are determined!!!

Mixing point: 2 variables (n2, n5)

2 balance equations (two species)
Degree of freedom = 0
Cooler: 2 variables (n2, n4)
2 balance equations (two species)
Degree of freedom = 0
Splitting point: 2 variables (n4, n5) Donot use SP in the solution

1 balance equation
CHBI 201 29
Degree of freedom = 1
EXAMPLE - continue
Overall DA balance:
0.96 n1 = 0.983 (100) n1 = 102.4 mol fresh feed
Overall mole balance:
n1 = n3 + 100 n3 = 2.4 mol H2O condensed
Mole balance on Mixing point:
n1 + n 5 = n 2
Water blance on Mixing point:
0.04n1 + 0.017n5 = 0.023n2

n2 = 392.5 mol
n5 = 290 mol recycled

CHBI 201 30
CHEMICAL REACTION STOICHIOMETRY
If there is a chemical reaction in a process
More complications

The stoichiometric ratios of the chemical reactions

Constraints

The stoichiometric equation 2SO2 + O2 2SO3

2 molecules of SO2 reacts with 1 molecule of O2 and yields 2
molecules of SO3

2, 1 and 2 are stoichiometric coefficients of a reaction

CHBI 201 31
LIMITING & EXCESS REACTANTS

If the reactants are not in stoichiometric proportion

one of them will be excess, the other will be limiting

[ (n ) - (n ) ]
Fractional excess of A A feed A stoich
(n )
A stoich.

moles reacted
Fractional conversion of A
moles fed

n -n
Extend of reaction () i i0

i

CHBI 201 32
EXAMPLE (pg 120)

C3H6 + NH3 + 3/2 O2 C3H3N + 3 H2O

Feed: 10 mol % of C3H6, 12 mole % NH3 and 78 mole % air
A fractional converison of limiting reactant = 30%
Taking 100 mol of feed as a basis, determine which reactant
is limiting, and molar amounts of all product gas constituents
for a 30% conversion of the limiting reactant.

100 mol nC3H6

0.1 mol C3H6/mol nNH3

REACTOR
0.12 mol NH3/mol nO2

0.78 mol air/mol nN2

0.21 mol O2/mol air nC3H3N

0.79 mol N2/mol air nH2O

CHBI 201 33
 EXAMPLE continue
Feed: nC3H6= 10 mole nNH3=12 mole nO2= 78.(0.21) =16.4 mole
nNH3/nC3H6= 12/10 = 1.2 NH3 is excess (stoich. 1)
nO2/nC3H6= 16.4/10 = 1.64 O2 is excess (stoich. 1.5)
(nNH3)stoich.= 10 mole (nO2)stoich.= 15 mole

Moles reacted
(% excess)NH3 = (12-10) /10 x 100 = 20% excess NH3 Moles fed

(% excess)O2 = (16.4-15) /15 x 100 = 9.3% excess O2

(nC3H6)out=0.7 x (nC3H6)0= 7 mole C3H6 (since the fractional conversion of C3H6 is 30%)

Extent of reaction = = 3 mole (since ni = ni0 + i => 7= 10 - 1. )

nNH3 = 12- =9 mole nO2=16.4 1.5.()= 11.9
nC3H3N= = 3 molenH2O=3.() = 9 mole
CHBI 201 34
nN2= (nN2)0=61.6 mole
CHEMICAL EQUILIBRIUM
If you are given a set of reactive species and reaction
conditions;
a) What will be the final (equilibrium) composition of
the reaction mixture?
b) How long will the system take to reach a specified
state short of equilibrium?
Chemical equilibrium thermodynamics & Chemical Kinetics

A reaction can be
Reversible
Irreversible

CHBI 201 35
EXAMPLE
CO (g) + H2O (g) CO2 (g) + H2 (g)
Given @ T=1105 K, K=1
nCO= 1 mol, nH2O= 2mol, initially no CO2 and H2
Calculate the equilibrium composition and the
fractional converison of the limiting reactant.

Equilibrium constant;
yCO2 y H 2
K(T) =
yCO y H 2O

CHBI 201 36
EXAMPLE continue
nCO = 1-e , nH2O = 2-e , nCO2 = e , nH2 = e

yCO = (1-e)/3 yH2O = (2-e)/3

yCO2 = e /3 yH2 = e /3

K(T) = (e)2 / (1-e) (2-e) = 1

e = 0.667 mole
yCO = 0.111 yH2O = 0.444
yCO2 = 0.222 yH2 = 0.222
Limiting reactant is CO. nCO = 1-0.667 = 0.333
Fractional conversion = (1-0.333) / 1 mol feed = 0.667
CHBI 201 37