

20 32
1.8
C = 6.7C
T
2
(80F) =
\


20 32
1.8
C = 26.6C
and T
2
T
1
= (26.6 (6.6))C = 33.3C
(b) T(C) = T(F) 1C = (80 20)F 1C = 33.3C
1.8F 1.8F
Celsius Kelvin Fahrenheit Rankine
Normal Boiling
Point of Water
373.15
Freezing Point
of Water
Absolute Zero
0
 273.15
100
273.15
0 0
32
212 671.7
491.7
 459.7
6
Example 0.5: Convert 1.053 kJ lb
m
1
F
1
, the specific heat capacity of water is into units of
kJ kg
1
C
1
.
Specific heat capacity relates to a change in temperature and therefore temperature differences, and
the conversion factor (1C 1.8F) should be used (and not equation 4).
1.053
kJ
lb
m
F
2.2046 lb
m
1 kg
1.8F
1C
= 4.18 kJ kg
1
C
1
In general, equations (1 to 5) should only be used to convert between different temperature scales
(e.g. converting a temperature in F to C), while the conversion factors should normally be used to
convert from quantities expressed in one unit of temperature to another (e.g. specific heat capacity
or other thermodynamic properties).
0.3 DIMENSIONAL HOMOGENEITY
Every valid equation must be dimensionally homogeneous: that is all additive terms on both sides
of the equation must have the same units. It is a good idea to check the consistency of the units in
any equation you derive in order to reduce errors.
Consider an equation such as:
C(m
3
s
1
) = 3{2 + D(m)} (8)
where C is a volumetric flowrate in m
3
s
1
and D is a length in units of m.
If the equation is valid, what are the units of the constants 3 and 2?
Only quantities of the same units (and thus dimensions) may be added to (or subtracted from)
one another.
The constant 2 therefore must have the same units as D (m) if the equation is valid. The right hand
side of the equation: 3(2 + D) must have the same units as C. The constant 3 therefore has the
units of m
2
s
1
.
7
Example 0.6: Derive an equation between C(ft
3
min
1
) and D(ft) from equation (8), where C(ft
3
min
1
) is the volumetric flowrate C(m
3
s
1
) expressed in ft
3
min
1
and D(ft) is length D(m)
expressed in ft. First we need to find a relationship between C in m
3
s
1
and C in ft
3
min
1
:
C(m
3
s
1
) = Cft
3
(0.3048)
3
m
3
1 min = 4.719 10
4
C(ft
3
min
1
) (A)
min (1)
3
ft
3
60 s
Similarly we can find a relations ship between D in m and D in ft:
D(m) = Dft 0.3048m = 0.3048 D(ft) (B)
1ft
In order to convert equation 8 into a relationship between C(ft
3
min
1
) and D(ft), we simply
substitute for C(m
3
s
1
) and D(m) using (A) and (B) above:
4.719 10
4
C(ft
3
min
1
) = 3{2 + 0.3048D(ft)}
Dividing through by 4.719 10
4
and taking 0.3048 out of the brackets on the right hand side we
obtain:
C(ft
3
min
1
) = 1938{6.562 + D(ft)} (C)
We can check the answer with an example: if D = 1 m, from (8) C = 9 m
3
s
1
. Now converting the
units of C and D we obtain C = 19070 ft
3
min
1
and D = 3.281 ft. Substituting D =3.281 ft into
(C) above we obtain C = 19071 ft
3
min
1
as before, confirming that the equation is correct (to four
significant figures).
A dimensionless quantity can be a pure number (e.g. 2, 1.3) or a combination of variables with no
net dimensions:
M(g)
M
0
(g)
D(cm)u(cm/s)(g/cm
3
)
[g/(cms)]
These combined quantities are called dimensionless groups.
Exponents (such as the 2 in x
2
), transcendental functions (such as log, exp and sin) and
arguments of transcendental functions (such as x in sin x) must be dimensionless quantities.
For example 10
2
is OK but 10
2C
is meaningless.
0.4 COMPOSITIONS OF MIXTURES
Chemical engineers rarely work with pure materials, we mostly work with mixtures. We therefore
need the ability to accurately and unambiguously define the compositions of any mixtures that we
work with. In some problems in the EBL problem book the feed composition is given in units of %
w/w. Percentages can also be expressed in moles or volumes and there are many other ways to
represent composition information. Where reactions are involved it is often necessary to work in
moles in order to handle the reaction stoichiometry. For liquids the most common units are mass
8
and mole fractions (or %w/w and mol%). In order to convert from mass fractions to mole fraction
the following equations is used:
Mole fraction of i =
(mass of i)
(M
W
of i)
j
(mass of j)
(M
W
of j)
(9)
Example 0.7: A hydrocarbon mixture has a composition of 3.9 % w/w H
2
, 40.2 % w/w CH
4
and
55.9 % w/w C
2
H
6
. What is its composition on a molar basis ?
The problem can be solved by setting out a table of the components, their molecular weights and
mass of each component in (say) 100g of the mixture. The number of moles of each component is
then calculated by dividing its mass by the molecular weight. The mole fraction of each
component is then computed from the ratio of the number of moles of that component to the total
number of moles.
M
W
mass(g) moles mole fraction
H
2
2 3.9 3.9/2 = 1.95 1.95/6.32 = 0.309
CH
4
16 40.2 40.2/16 = 2.51 2.51/6.32 = 0.397
C
2
H
6
30 55.9 55.9/30 = 1.86 1.86/6.32 = 0.294
100.0 6.32 1.000
Concentrations are sometimes used for liquids, and these can be expressed either as molar or mass
concentrations (moles per unit volume e.g. molarity mol l
1
or mass per unit volume
e.g. mg l
1
). For gases volume concentration or volume fraction is often used. This is defined as:
v
i
=
volume of component i
total volume of mixture
(10)
%v/v = = 100 v
i
(11)
where the volume of component i is the volume that would be occupied by the pure component i
which is present in the mixture, at the same temperature and pressure as the mixture. The volume
fraction of a component is equivalent to its mole fraction for ideal gases (see section on partial
pressures below).
It is sometimes useful to use the average molecular weight of a mixture, which is the ratio of the
mass of a sample of the mixture to the number of moles of all species in the sample. In Example
0.1 above the average molecular weight of the hydrocarbon mixture can be obtained from the table
as
W
M = 100.0/6.32 = 15.8 g mol
1
. In general the average molecular weight can be calculated
from:
W
M =
i
y
i
M
i
(12)
9
where y
i
and M
i
are the mole fraction and molecular weight respectively of the ith component.
Example 0.8: Calculate the average molecular weight of air from its approximate composition of
79% N
2
and 21% O
2
.
W
M = 0.79 mol N
2
28 g N
2
+ 0.21 mol O
2
32 g O
2
= 29 g mol
1
mol mol N
2
mol mol O
2
0.4.1 Component Free Units e.g. composition on a dry basis
Common techniques for the analysis of gases frequently provide compositions on a dry basis
indicating the composition of the gas without water. For example a gas which contains 33.3 mole%
CO
2
, 33.3% N
2
and 33.3% H
2
O contains 50 % CO
2
and 50% N
2
on a dry basis.
Example 0.9: A stack gas contains 60.0 mole% N
2
, 15.0% CO
2
, 10% O
2
and the balance H
2
O.
Calculate the molar composition of the gas on a dry basis.
moles moles (dry basis) mole% (dry gas)
N
2
60.0 60.0 100%60.0/85.0 = 70.6
CO
2
15.0 15.0 100%15.0/85.0 = 17.6
O
2
10.0 10.0 100%10.0/85.0 = 11.8
H
2
O 15.0
100.0 85.0
Example 0.10: A stack gas analysis gives a dry basis composition of 65% N
2
, 14% CO
2
, 11% CO
and 10% O
2
. A humidity measurement shows that the mole fraction of H
2
O in the stack gas is
0.0700. Calculate the stack gas composition on a wet basis.
Consider 100 moles of wet gas. This will contain 7.0 moles of water and 93 moles of dry gas.
Moles mole%(dry basis) moles (wet) mole% (wet)
N
2
65 0.6593.0 = 60.45
CO
2
` 93.0 14 0.1493.0 = 13.02
CO 11 0.1193.0 = 10.23
O
2
)
10 0.1093.0 = 9.30
H
2
O 7.0 7.00
100.0 100.00
10
0.4.2 Partial pressures and Daltons law
The partial pressure of a component in a gas mixture (p
i
) is that pressure which the component
would exert if present alone in the same volume as occupied by the mixture and at the same
temperature T. For ideal gases, the partial pressure of a gas can be used as a measure of
composition. All pure gases and gaseous mixtures can be assumed to behave ideally up to a
pressure of 10atm, so that
PV = nRT (13)
where the universal gas constant R = 8.3143 kJ kmol
1
K
1
. At standard temperature and pressure
(STP, 0C and 1atm) this gives a standard molar volume V/n of 22.414 m
3
kmol
1
.
Aside: It is often necessary to calculate the volume of a gas V at a temperature T and pressure P. A
good way of doing this is to apply the ideal gas law in the form:
P
1
V
1
T
1
=
P
0
V
0
T
0
= nR
so that
V
1
= V
0
P
0
P
1
T
1
T
0
= n22.414m
3
/kmol
P
0
P
1
T
1
T
0
(14)
where subscript zero indicates standard conditions. This avoids the need to correct units of
pressure.
Example 0.11: The volume of a balloon is found to be 2.50 litres at 25C and 765 mm Hg.
Estimate the volume of the balloon at STP and in the Sahara desert where the pressure and
temperature are 750 mm Hg and 45C
At STP V
0
= 2.5 litres 765 mm Hg 273.15 K = 2.31 litres
760 mm Hg 298.15 K
In the desert
V
1
= 2.5 litres 765 mm Hg 318.15 K = 2.72 litres
750 mm Hg 298.15 K
Consider a gaseous mixture consisting of n
A
kmol of component A, n
B
kmol of component B and n
C
kmol of component C at a total pressure P and absolute temperature T. The ideal gas law gives
PV = (n
A
+ n
B
+ n
C
)RT (15)
where V is the volume of the mixture. The definition of partial pressure gives
P
A
V = n
A
RT (16a)
P
B
V = n
B
RT (16b)
P
C
V = n
C
RT (16c)
11
Summing these three equations and comparing with equation (15) gives Daltons law
P = P
A
+ P
B
+ P
C
(17)
The total pressure of a gaseous mixture is the sum of the partial pressures of the component gases.
Dividing equation (16a) by equation (15) gives a more useful formulation of Daltons law
P
A
= y
A
P (18)
Equation (18) is important and useful, but is often forgotten or misunderstood.
For volume fractions we can write
Pv
A
= n
A
RT (19)
and dividing by equation (13) we obtain
volume fraction of A =
v
A
V
=
n
A
n
= y
A
(20)
Example 0.12: A mixture of acetone and nitrogen at a temperature of 35C and pressure of 6.3 atm
gauge is flowing at a rate of 1.2 m
3
s
1
. If the partial pressure of acetone in the stream is p
A
= 501
mm Hg and the ambient pressure is 765 mm Hg determine the flow rate of acetone in kmol min
1
.
First obtain total molar flow rate n using equation 14.
1.2 m
3
s
1
= n
22.414m
3
kmol
760 mmHg
(765 + 6.3760)mmHg
308.15K
273.15K
n = 1.2 m
3
273.15K 5553 mm Hg 1 kmol 60s = 20.8 kmol min
1
s 308.15K 760 mm Hg 22.414m
3
1min
p
A
= y
A
P =
n
A
n
P n
A
=
p
A
P
n
n
A
= 501 mm Hg 20.8 kmol = 1.88 kmol min
1
5553 mm Hg min
12
APPENDIX 0.1: CONVERSION FACTORS
Length: 1 m = 3.281 ft
= 1.094 yd
= 6.21410
4
mile
Volume: 1 m
3
= 35.31 ft
3
= 264.2 US gal
= 6.29 bbl (barrel)
= 220 Imp. gal
= 1000 litres
Mass: 1 kg = 2.205 lb
m
= 9.8410
4
ton (or long ton)
= 110
3
tonne (or metric tonne)
= 1.54310
4
grain
= 0.01968 cwt
Force: 1 N = 1 kgm s
2
= 110
5
dyne (gcm s
2
)
= 0.2248 lb
f
Pressure: 1 N m
2
= 1 Pa = 1 kg m
1
s
2
= 1.45010
4
lb
f
in
2
(psi)
= 9.86910
6
atm
= 110
5
bar
= 7.5010
3
mm Hg or torr
Energy: 1 J = 9.47810
4
Btu
= 2.77810
7
kWhr
= 0.2388 cal
= 10
7
erg (gcm
2
s
2
or dynecm)
Power: 1 W = 1.36010
3
hp
Temperature: T(F) = 1.8 T(C) + 32
T(K) = T(C) + 273
T(R) = T(F) + 459
Viscosity: 1 kg m
1
s
1
= 1 Pas = 1000 centipoise
Amount of material: 1 mole (gmole) = 2.20510
3
lbmole
= 110
3
kmol (kgmole)
13
A FEW PROBLEMS TO TEST YOURSELF:
1. Unit conversion (Section 1 & 2):
(a) There must be millions of milliseconds in a week. How many are there?
(b) We are travelling at a staggering 38.1 feet per second announced the train driver. How
fast is the train travelling in mph?
(c) Convert 554 m
4
day
1
kg
1
into cm
4
min
1
g
1
.
(d) An American customer asks The density of your product is 921 kg m
3
, whats that in lb
m
ft
3
? What is your reply?
2. (Section 2.1) A pressure gauge indicates that the pressure inside a reaction vessel is 312.2 psig.
If the barometric pressure is 753 mm Hg what is the vessel's absolute pressure in kPa?
3. (Sections 1 & 2) You find a useful equation in an old text book. There is a sample calculation,
but you suspect that the value of the Universal gas constant used (0.073 atm ft
3
lbmol
1
R
1
) is
wrong. What is the correct value in these units (atm ft
3
lbmol
1
R
1
)? [R = 8.314 J mol
1
K
1
]
4. (Section 4) A gaseous mixture at 3 barg contains 32.9 mol% He, 40.7 mol% N
2
and 26.4 mol%
Ar. What is the composition of this mixture on a mass basis? If the barometric pressure is 758
mm Hg, what is the N
2
partial pressure p
N
2
?
MW (He) = 4.003 MW (N
2
) = 28.02 MW (Ar) = 39.95
5. (Section 4) A fuel has the following composition on a molar basis: 40.0% CH
4
,
24.0% C
2
H
4
, 16% C
3
H
8
, 10% CO
2
, 10% H
2
O. What is the composition of the fuel on a dry
basis? What is the composition of the fuel on a mass basis? What is the average molecular
weight of the fuel? [Relative atomic masses: O = 16, C = 12, H = 1]
6. (Section 2.2):
(a) Convert the temperature T = 85F to R, C, and K
(b) Convert the temperature difference T = 85C to K, F, and R
7. (Section 3) A seed crystal of diameter D(mm) is placed in a solution of dissolved salt, and new
crystals are observed to nucleate (form) at a constant rate r(crystals min
1
). Experiments with
seed crystals of different sizes show that the rate of nucleation varies with the seed crystal
diameter as
r(crystals min
1
) = 200D + 10D
2
where D is in mm.
(a) What are the units of the constants 200 and 10?
(b) Calculate the crystal nucleation rate in crystals s
1
for to a seed crystal diameter of 0.05inch.
(c) Derive a formula for r(crystals s
1
) in terms of D(in). Check the formula with the
result of (b).
14
Answers:
1. (a) 6.0510
8
ms (b) 26.0 mph (c) 38,500 cm
4
min
1
g
1
(d) 57.5 lb
m
ft
3
2. 2253 kPa
3. 0.730 atm ft
3
lbmol
1
R
1
4. 5.7 %w/w He, 49.0 %w/w N
2
, 45.3 %w/w Ar, p
N
2
= 1.63 . 10
5
N m
2
5. 44.4 mol% CH
4
dry basis, 24.3 %w/w CH
4
, average molecular weight 26.4.
6. (a) 544R, 29C, 303K (b) 85K, 153F, 153R
7. (a) 200 crystals min
1
mm
1
, 10 crystals min
1
mm
2
(b) 4.5 crystals s
1
(c) r(crystals s
1
) = 84.67D + 107.53D
2