Periodic Table of the Elements

Period
Group**

1
IA
1A
18
VIIIA
8A
1
1
H
1.008
2
IIA
2A
13
IIIA
3A
14
IVA
4A
15
VA
5A
16
VIA
6A
17
VIIA
7A
2
He
4.003
2
3
Li
6.941
4
Be
9.012
5
B
10.81
6
C
12.01
7
N
14.01
8
O
16.00
9
F
19.00
10
Ne
20.18
3
11
Na
22.99
12
Mg
24.31
3
IIIB
3B
4
IVB
4B
5
VB
5B
6
VIB
6B
7
VIIB
7B
8 9 10
11
IB
1B
12
IIB
2B
13
Al
26.98
14
Si
28.09
15
P
30.97
16
S
32.07
17
Cl
35.45
18
Ar
39.95
------- VIII -------
------- 8 -------
4
19
K
39.10
20
Ca
40.08
21
Sc
44.96
22
Ti
47.88
23
V
50.94
24
Cr
52.00
25
Mn
54.94
26
Fe
55.85
27
Co
58.47
28
Ni
58.69
29
Cu
63.55
30
Zn
65.39
31
Ga
69.72
32
Ge
72.59
33
As
74.92
34
Se
78.96
35
Br
79.90
36
Kr
83.80
5
37
Rb
85.47
38
Sr
87.62
39
Y
88.91
40
Zr
91.22
41
Nb
92.91
42
Mo
95.94
43
Tc
(98)
44
Ru
101.1
45
Rh
102.9
46
Pd
106.4
47
Ag
107.9
48
Cd
112.4
49
In
114.8
50
Sn
118.7
51
Sb
121.8
52
Te
127.6
53
I
126.9
54
Xe
131.3
6
55
Cs
132.9
56
Ba
137.3
57
La*
138.9
72
Hf
178.5
73
Ta
180.9
74
W
183.9
75
Re
186.2
76
Os
190.2
77
Ir
190.2
78
Pt
195.1
79
Au
197.0
80
Hg
200.5
81
Tl
204.4
82
Pb
207.2
83
Bi
209.0
84
Po
(210)
85
At
(210)
86
Rn
(222)
7
87
Fr
(223)
88
Ra
(226)
89
Ac~
(227)
104
Rf
(257)
105
Db
(260)
106
Sg
(263)
107
Bh
(262)
108
Hs
(265)
109
Mt
(266)
110
---
()
111
---
()
112
---
()
114
---
()
116
---
()
118
---
()
Lanthanide Series*
58
Ce
140.1
59
Pr
140.9
60
Nd
144.2
61
Pm
(147)
62
Sm
150.4
63
Eu
152.0
64
Gd
157.3
65
Tb
158.9
66
Dy
162.5
67
Ho
164.9
68
Er
167.3
69
Tm
168.9
70
Yb
173.0
71
Lu
175.0
Actinide Series~
90
Th
232.0
91
Pa
(231)
92
U
(238)
93
Np
(237)
94
Pu
(242)
95
Am
(243)
96
Cm
(247)
97
Bk
(247)
98
Cf
(249)
99
Es
(254)
100
Fm
(253)
101
Md
(256)
102
No
(254)
103
Lr
(257)
1
1. Introduction to Chemical Engineering Operations
Evaporation Definition & Purpose:
Evaporation is a special case of heat transfer to a boiling liquid. This particular heat transfer
application is so common and important that it is treated as a separate unit operation.
The intent is to concentrate a non-volatile solute from a solvent, usually
water. Boiling off the solvent does this. Concentration by evaporation is
normally stopped before the solute begins to precipitate; if not, the operation
is better considered as crystallization.
Evaporation is usually treated as the separation of a liquid mixture into a
liquid product (concentrate or thick liquor) and a vapor byproduct, although
in some special cases, notably water treating and desalination, the vapor is the
product instead of the thick liquor.
Principle of Operation. The driving force for heat transfer is the difference in temperature between
the steam in the coils and the product in the pan. The steam is produced in large boilers, generally
tube and chest heat exchangers. The steam temperature is a function of the steam pressure. Water
boils at 100 C at 1 atm., but at other pressures the boiling point changes. At its boiling point, the
steam condenses in the coils and gives up its latent heat. If the steam temperature is too high, burn-
on/fouling increases so there are limits to how high steam temperatures can go. The product is also at
its boiling point. The boiling point can be elevated with an increase in solute concentration. This
boiling point elevation works on the same principles as freezing point depression
In this course, we will limit evaporation to systems with non-volatile solutes.
Evaporation is similar to drying in that both drive off volatiles, but is different in that the product is a
liquid. Evaporation differs from distillation because both components in a distillation system are
volatile. Evaporation normally produces a single vapor fraction, distillation several.
Evaporators are classified by the number of effects. In a single-effect evaporator, steam provides
energy for vaporization and the vapor product is condensed and removed from the system. In a
double-effect evaporator, the vapor product off the first effect is used to provide energy for a second
vaporization unit. This cascading of effects can continue for many stages. Multiple-effect evaporators
can remove much larger amounts of solvent than is possible in a single effect.
Because many materials cannot tolerate high temperatures, evaporators often operate at reduced
pressure so that the boiling point will also be reduced.
In many (most?) cases, evaporators operate under a vacuum. This means that a vacuum pump or jet
ejector vacuum system is required on the last effect.
Evaporators are commonly used in the inorganic and organic chemical, pulp and paper, and food
industries (especially sugar). Examples are the concentration of fruit juices and of NaOH.
2
Types of Evaporator:
Evaporator Designs
Types of single effect evaporators:
Batch Pan
Rising film
Falling film
Plate evaporators
Scraped surface
Batch pan evaporators are the simplest and oldest. They consist of spherical shaped, steam jacketed
vessels. The heat transfer per unit volume is small requiring long residence times. The heating is due
only to natural convection; therefore, the heat transfer characteristics are poor. Batch plants are of
historical significance; modern evaporation plants are far-removed from this basic idea. The vapours
are a tremendous source of low-pressure steam and must be reused.
Rising film evaporators consist of a heat exchanger isolated from the vapour separator. The heat
exchanger, or calandria, consists of 10 to 15 meter long tubes in a tube chest, which is heated with
steam. The liquid rises by percolation from the vapours formed near the bottom of the heating tubes.
The thin liquid film moves rapidly upwards. The product may be recycled if necessary to arrive at the
desired final concentration. This development of this type of modern evaporator has given way to the
falling film evaporator.
The falling film evaporators are the most widely used in the food industry. They are similar in
components to the rising film type except that the thin liquid film moves downward under gravity in
the tubes. A uniform film distribution at the feed inlet is much more difficult to obtain. This is the
reason why this development came slowly and it is only within the last decade that falling film has
superceded all other designs. Specially designed nozzles or spray distributors at the feed inlet permit
it to handle more viscous products. The residence time is 20-30 sec. as opposed to 3-4 min. in the
rising film type. The vapour separator is at the bottom, which decreases the product hold-up during
shut down. The tubes are 8-12 meters long and 30 -50 mm in diameter.
Performance Measures:
There are three main measures of evaporator performance:
1. Capacity (kg vaporized / time)
2. Economy (kg vaporized / kg steam input)
3. Steam Consumption (kg / hr)
Note
that the measures are related, since Consumption = Capacity/Economy.
3
Economy calculations require enthalpy balances.
Distillation
Distillation is by far the most predominant separation technique used in the chemical process industry.
Distillation is a cascade of equilibrium stages at which the vapor mixture is in equilibrium with the
liquid mixture. An in-depth understanding of vapor-liquid equilibrium (VLE) is therefore essential to
the understanding and design of distillation processes.
The process of distillation should be familiar to most readers. The basic concept is that we can
separate a mixture of two pure liquids with different boiling points by heating the mixture to a
temperature between their respective boiling points. For example, water boils at 100C and ethanol
boils at around 83C at atmospheric pressure. If we heat the mixture to say 92C, the ethanol will boil
and be transformed into vapour (which is collected and condensed) while the water will remain as a
liquid. This phenomenon is usually quantified by the relative volatility of the two components.
A distillation column is used to make this process more efficient.
Vapor-liquid-equilibrium is taught in the chemical engineering curriculum at various levels. Generally
a simple Raoult's law approach is taught early in material and energy balance classes.
Importance of VLE
Vapor-liquid equilibrium (VLE) under grids the bulk of
industrial separation processes, particularly in distillation
processes. In this module, we will consider only binary (two-
component) mixtures. The composition of the liquid phase
will be designated by the mole fraction of the more volatile
component (lower boiling point), represented by x. The mole
fraction of the other component is of course 1- x. Likewise,
the mole fraction of the vapor will be represented by y, with 1 -
y being the composition of the other component in the vapor
phase. When the liquid mixture is heated to its boiling point, the vapor produced will, in general, have
a different composition than the liquid; i.e., x <> y.
Thus, boiling the mixture produces a partial separation of the components occurs. If the vapor is
collected, it can be condensed and boiled again to further change the composition.
4
Distillation columns use this principle effectively repeating the separation
process at individual trays within a column. Such columns may have over a
hundred trays on which VLE is occurring. Depicted at the right is a cartoon
cut-away of a small section of a tray-type distillation column. Two sieve trays
are shown. Hot vapor flows up through the holes in the sieve tray and
vigorously bubbles through the liquid. The vapor and liquid mix on this tray
and the new mixture boils. The composition of the liquid, x, leaving the will be
enriched in the less volatile component while the composition of the vapor, y,
will be enriched in the more volatile component. The vapor rises up to the next tray where it will
contact a liquid of larger x and mixing and re-equilibration will again occur. The liquid leaving the
tray will flow over the weir and down the downcomer to the next tray where it will mix with the vapor
on that tray. In this way, x tends to become smaller at each lower tray, while y tends to increase at
each tray higher in the column. VLE refers to the relationship between the x and y values on each
tray.
At equilibrium, the temperature and pressure of the liquid and vapor phases will be equal, but the
compositions will not. Why is this? There are two main factors that make the vapor and liquid
compositions different at equilibrium: the pure component vapor pressures and the non idealities in
the liquid phase.
Crystallization
Widely used crystallizer type(Swenson Draft tube)
Crystallization is the formation of solid particles from liquid or from vapor
phase. It is unit operation, where separation of a desired component and the
phase change simultaneously takes place. The driving force in
crystallization is the super saturation, which discharges as crystals to the
solid phase. Super saturation is mainly accomplished by evaporation or by
cooling the liquid in bulk crystallizers. The most important targets in
crystallization are to get pure crystals with a desired product crystal size
distribution in the chemical, medical and in food industries
Crystallization refers to the formation of solid crystals from a homogeneous solution. It is
essentially a solid-liquid separation technique and a very important one at that.
Example of Crystallization
1. Water freezing
2. Removing sucrose from beet solutions
3. Removing KCl from an aqueous solution
Crystals are grown in many shapes, which are dependent upon downstream processing or final
product requirements. Crystal shapes can include cubic, tetragonal, orthorhombic, hexagonal,
monoclinic, triclinic, and trigonal. In order for crystallization to take place a solution must be
5
"supersaturated". Super saturation refers to a state in which the liquid (solvent) contains more
dissolved solids (solute) than can ordinarily be accommodated at that temperature.
So how do you grow crystals? Let's consider an example that is fairly easy to envision. Take a pot
of boiling water and add table salt while stirring to make a water-salt solution. Continue adding salt
until no more salt will dissolve in the solution (this is a saturated solution). Now add one final
teaspoon of salt. The salt that will not dissolve will help the first step in crystallization begin. This
first step is called "nucleation" or primary nucleation. The salt resting at the bottom of the pot will
provide a site for nucleation to occur. Primary nucleation is the first step in crystallization. Simply
defined, it's the growth of a new crystal
On an industrial scale, a large super saturation driving force is necessary to initiate primary
nucleation. The initiation of primary nucleation via this driving force is not fully understood which
makes it difficult to model (experiments are the best guide). Usually, the instantaneous formation of
many nuclei can be observed, "crashing out" of the solution. You can think of the super saturation
driving force as being created by a combination of high solute concentration and rapid cooling. In the
salt example, cooling will be gradual so we need to provide a "seed" for the crystals to grow on. In
continuous crystallization, once primary nucleation has begun, the crystal size distribution begins to
take shape
The second chief mechanism in crystallization is called secondary nucleation. In this phase of
crystallization, crystal growth is initiated with contact. The contact can be between the solution and
other crystals, a mixer blade, a pipe, a vessel wall, etc. This phase of crystallization occurs at lower
super saturation (than primary nucleation) where crystal growth is optimal. Secondary nucleation
requires "seeds" or existing crystals to perpetuate crystal growth. In our salt example, we bypassed
primary nucleation by "seeding" the solution with a final teaspoon of salt. Secondary nucleation can
be thought of as the workhorse of crystallization.
We've discussed how crystallization occurs once super saturation is reached, but how do we
reach super saturation? We have already covered one such method in our salt crystallization
example. Since the solubility of salt in water decreases with decreasing temperature, as the solution
cools, its saturation increases until it reaches super saturation and crystallization begins. Cooling is
one of the fore most common methods of achieving super saturation. It should be noted that
cooling will only help reach super saturation in systems where solubility and temperature are
directly related. Although this is nearly always the case, there are exceptions.
The most common methods of reaching super saturation in industrial processes are:
1. Cooling (with some exceptions)
2. Solvent Evaporation
3. Drowning
4. Chemical Reaction
In an industrial setting, the solute-solvent mixture is commonly referred to as the "mother liquor".
6
Drowning describes the addition of a non solvent to the solution which decreases the solubility of
the solid. A chemical reaction can be used to alter the dissolved solid to decrease its solubility in the
solvent, thus working toward super saturation. Each method of achieving super saturation has its own
benefits. For cooling and evaporative crystallization, super saturation can be generated near a heat
transfer surface and usually at moderate rates. Drowning or reactive crystallization allows for
localized, rapid crystallization where the mixing mechanism can exert significant influence on the
product characteristics.
Extraction (Liquid extraction)
A process in which a liquid mixture of two species (the solute and the feed carrier) is contacted in a
mixer with a third liquid (the solvent) that is immiscible or nearly miscible with the feed carrier.
When the liquids are contacted the solute transfers from the feed carrier to the solvent. The combined
mixture is then allowed to settling to two phases that are then separated by gravity in a decanter.
Separation of solid or liquid compounds with significantly different solubility properties. Compounds
in a mixture are separated by there differential solubility in two immiscible solvents (one usually
water )
Drying
A process in which a wet solid is heated or contacted with a hot gas
stream, causing some or all of the liquid wetting the solid to evaporate.
The vapor and the gas it evaporates into, emerge as one outlet
stream and the solid and remaining residual liquid emerge as a
second outlet stream
Dimensions and Units
Dimensions
mental concepts used to distinguish between opposing sense perceptions
length (L), mass (m), time (t), temperature (T), amount of substance (n)
fundamental dimensions - a base set from which all others can be derived
Example. What are the dimensions of mass flux (mass flow rate per unit area
perpendicular to the flow)?
G
A
dm
dt

1
dimensions are
m
L t
2
Units
scales used to quantify dimensions in a standard way
SI system is now almost universally accepted
7

the American engineering system (based on British standards) is still used
extensively in the U.S.
SI System - Base Units for Some of the Fundamental Dimensions
meter (m) - a length equal to 1650763.73 wavelengths of the radiation given off by a krypton-
86 atom when a specific electronic transition takes place
kilogram (kg) - mass of the international prototype kilogram
second (s) - time equal to the duration of 9192631770 periods of the radiation corresponding to
a specific cesium-133 atom transformation
kelvin (K) - a temperature increment equal to 1/273.16 of the thermodynamic temperature of
the triple point of water
mole (mol) - the amount of substance of a system which contains as many elementary entities
as there are carbon atoms in 0.012 kg of carbon-12
SI System - Some Derived Units
1 N (newton) = 1 kg m s
-2
unit of force (ma)
1 J (joule) = 1 N m = 1 kg m
2
s
-2
unit of energy/work (Fx)
1 W (watt) = 1 J s
-1
= 1 kg m
2
s
-3
unit of power (dW/dt)
1 Pa (pascal) = 1 N m
-2
= 1 kg m
-1
s
-2
unit of pressure (F/A)
Dimensional Homogeneity and Dimensionless Quantities
All additive terms on both sides of an equation must have the same units.
Dimensionless numbers have no net units.
Dimensionless groups are dimensionless numbers formed by a combination of variables.
Care must be taken in converting dimensional equations to a different set of units.
Example: The vapor pressure p
*
(in units of mmHg) of water is given as a function of
temperature T (in units of
o
C) by the following equation:
0 . 228
21 . 1668
96681 . 7 log
*
10
+

T
p
8
To convert this to an equation for vapor pressure (in units of bar) as a function of temperature
(in units of K), first write conversion equations for p* and T, as follows
15 . 273 ) ( ) (
) ( 062 . 750
01325 . 1
760
) ( ) (
* * *


K T C T
bar p
bar
mmHg
bar p mmHg p
o
Now, substitute these into the
original equation and simplify as desired
2 . 45 ) (
21 . 1668
0917 . 5
2 . 45 ) (
21 . 1668
) 062 . 750 ( log 9668 . 7 ) ( log
0 . 228 15 . 273 ) (
21 . 1668
9668 . 7 )] ( 062 . 750 [ log
10
*
10
*
10

+

K T
K T
bar p
K T
bar p
How would you check to see if this is correct? You may know that the "normal boiling point" of
water is 100 oC, thus, the vapor pressure of water is 1 atmosphere (1.01325 bar) at 100 oC (373.15
K). Does the above equation give this answer correctly? If it is close, what is the percentage
error?
Significant Figures
Examples. 1532 or 3980. 4 significant figures
1530 or 9.81x10
5
3 significant figures
1532.0 or 4.7835x10
2
5 significant figures
( . )( . )
( . )
.
321 4 372
10815
130
not 1.298, 1.2977, etc.
1.76 + 3.295 = 5.06 not 5.055, etc.
Precision of a measurement is the reproducibility of the measurement, which is expressed as some
kind of deviation from the mean of a set of measurements, and it reflects random errors in the
measurement.
Accuracy of a measurement is the estimated maximum deviation from the true value, and accounts
for both random and systematic errors.
The number of significant figures used to represent an experimentally known quantity should reflect
the accuracy with which the information is known.
Example. A velocity reported as 2.51 cm/s indicates that the true velocity is believed to be between
2.505 and 2.515 cm/s.
An exact number can be used as if it had an infinite number of significant figures. For example, in
the units relationship 1 atm = 14.696 psi, the number 1 is assumed to be an exact number, i.e., it does
9
not restrict the number of significant figures in any calculation using this units conversion factor.
This means that 1 atm is really 1.00000.. atm, however, 14.696 is listed to only 5 significant
figures. The numbers of significant figures listed in the text for unit conversions are sufficient for
most chemical engineering calculations. The first number listed is assumed "exact". Sometimes it is
not obvious which other numbers are assumed to be exact (e.g., 760 mm Hg, 1.01325 bar, etc.). If in
doubt, and if it is important to your engineering calculation, you should check with an appropriate
reference.
Ex: 1 ft = 12 in (both exact numbers)
1 m = 100 cm (both exact numbers)
1 in = 2.54 cm (1 exact, 2.54 to 3 sig. figs.)
1 bar = 10
5
Pa (both exact numbers)
1 W = 1 N m (both exact numbers)
1 W = 9.486x10
-4
Btu/s (1 exact, 9.486 to 4 sig. figs.)
Processes and Process Variables
Density and Related Quantities
Basic Concepts
average density
m
V
point density

lim

V
m
V
V
Note:
V
is a volume that is very small compared to the size of the system, but large enough to
contain a very large number of molecules.
Note: If the density is constant over a region of space, then the point density is equal to the
average density at all points.
Dimensions of density (m/l
3
)
Units of density (kg/m
3
, g/cm
3
, lb/ft
3
, etc.)
Related quantities molar density (n/V = /M)
specific volume (V/m = 1/)
molar volume (V/n = M/)
Densities of Solids
10
Often measured by weighing a chunk of the solid in air and in water:
) m m (
m
) water in ( m ) air in ( m
) air in ( m ) water (
) water displaced ( V
) air in ( m
V
m
W A
A
W

For packed beds of solids, containing void spaces:

B
bulk density
total mass solids
total bed volume

Specific gravity is defined as the ratio of the actual density of a solid (or liquid) to the density of a
reference substance (usually liquid water at 4
o
C, 1 atm, where = 1.000 g/cm
3
).
Densities of Liquids
Methods of measurement:
hydrometer - uses Archimedes' principle - example of special scale
o
o
o
API
SG
F
F

1415
60
60
1315
.
.
(API Gravity)
Determine volume and mass separately - an example is a pycnometer
Special instrumentation - an example is the vibrating tube method
Densities of Gases
Prediction from pressure, temperature, and composition
SG
std conditions
air std conditions
M

( . )
( , . ) . 29 0
Species Volume % = Mole %
N
2
78.09
O
2
20.95
Ar 0.93
CO
2
0.03
100.00
+ Traces of Ne, He, CH
4
, Kr, H
2
, Xe, O
3
, etc.
11
Note: Air almost always contains significant amounts of water vapor (humidity), as well as
some particulates and other pollutants (e.g., NO). Amounts depend on local conditions.
Combustion air - taken as 79.0 % atmospheric N
2
" + 21.0 % O
2
Molecular Weight and Amount of Substance
molecular weight = (mass)/(amount of substance) = (mass)/(number of moles)
M
m
n
(units = g/mol, kg/kmol, lb/lbmol)
Note: In chemical engineering, "amount of substance" is often called "number of moles".
Molecular weight = sum of atomic weights
Basis: atomic weight of
12
C = 12 (exactly)
Atomic weight of naturally occurring C = 12.01115
1 mol = 6.023 x 10
23
molecules (Avogadros number)
Units and Dimensions. Units are basic concepts of measurements and units are means of expressing
dimensions.
Take care of your units, units take care of you
Dimensions Units
Length m, ft
Time hr, s
Mass kg, Ton
Conversion of Units. The equivalence between two expressions of the same quantities may be
defined in terms of ratio:
(1 cm/10 mm) 1 centimeter per 10 millimeter
(10 mm/1 cm) 10 millimeter per 1 centimeter
The above ratios are called conversion factors. (new unit /old unit)
1.1 Convert 36 mg to grams:
36 mg 1 g
12
= 0.036
g
1000
mg

1.2 The order is to give Demerol (merperidine) 35 mg, IM q4h p.r.n. for pain. The medication
is supplied in an ampule marked 50 mg per 1.0 ml. How many milliliters should u give?
X ml = 35 mg/dose
Conversion factor to convert milligrams to milliliters; 1 ml = 50 mg
Put in to equation, in the form of the conversion factor that will cancel the unwanted labels and
leave the desired label on both sides of the equation with equal sign.
35 mg 1 ml
= 0.7 ml/dose
dose 50 mg
Therefore 0.7 ml will provide the ordered dose.
1.3 The order is to give 1/8 g of morphine sulfate IM q4h p.r.n for pain. On hand are ampules
labeled 10 mg per ml. How many milliliters should u give?
X ml = (1/8) g,
Conversion factors: 1 g = 1000 mg 10 mg = 1 ml
1/8 g 1 ml
1000
mg
=12.5 ml/dose
dose 10 mg 1 g
Therefore 12.5 ml will provide the ordered dose.
1.4 Convert 1 cm/s
2
to km/yr
2
1 cm 3600
2
s
2
24
2
hr
2
365
2
days
2
1 m 1 km
s
2
1
2
hr 1
2
day 1
2
yr
2
100
cm
= 9.95 x 10
9
km/yr
2
1.5 Convert 500 Btu/ft
2
s
0
F to g Cal/ cm
2
s
0
C
1.6 Convert 50 L/m
2
hr of CO
2
at NTP to m
3
/cm
2
s at 1.0 atm. And 50
0
C
13
Pressure. At sea level atmosphere pressure of 760 mm Hg is a standard pressure.
Absolute pressure means reference pressure at which pressure is zero perfect vacuum. Gage pressure
is relative to atmosphere pressure. Gage pressure zero means 1.0 atmosphere

P
abs
= P
gage
+ P
atm.
Negative gage pressure means abs. Pr.< atm. Pr.
For example, 1.0 cm Hg (75.0 cmHg) may also be called 1.0 cm vacuum.
Pressure is
force per unit area
a fluid exerts a pressure on the wall of its container
due to molecules bouncing off the wall
measured by determining force and area
Hydrostatic Pressure -- pressure difference between bottom and top of a column of fluid of
height h -- based on Newton's law of gravity
gh A F P
g Ah g m F
mg ma F

/
) ( ) (
Note: This is often written with a g
c
in the denominator, but it is only to remind you to watch out for
the units when using the American Engineering System of units!
barometer = an instrument for measuring atmospheric pressure
(1.000000 atm = 760.000 mmHg(0
o
C, std. g
o
)
Correction of a mercury barometer for temperature and location:
( )
[ ]
P gh g h
h
g
g
h
g
g
T T h
Hg C
g m s
T C
o o o
o
o o o
o
o
o
o
o

1
0 000182
9 80665
0
1
1
( ) .
.
differential manometer = an instrument for measuring differences in pressure
14
P g h
M
( )
1.7 In double effect evaporator, the 2nd effect is maintained under vacuum of 475 torr. Find P
abs
in kPa?
P
abs
= P
atm
P
vac

= 760 475 =285 torr; = 38 kPa

Temperature
Basis for Measurement (Zeroth Law of Thermodynamics)
thermal equilibrium is independent of the nature of systems
temperature is a property that tells us if two systems are in thermal equilibrium
measuring devices are systems that can be brought to thermal equilibrium with
the system of interest (hopefully without disturbing this system)
examples are liquid in glass thermometers, thermocouples, resistance
thermometers, bimetallic thermometers, radiation pyrometers, etc.
Celsius Scale T
freezing H2O
= 0
0
C T
boiling H2O
=100
0
C
Absolute zero means theoretically lowest attainable temperature, -273
0
C
Fahrenheit Scale T
freezing H2O
= 32
0
F T
b
= 212
0
F
T (K) = T(
0
C) + 273.15 and T(
0
R) = T(
0
F) + 459.67
NOTE: T(
0
F) = a .T(
0
C) + b
32 = a.(0) + b
212 = a(100) + b solving for a and b, a =1.8 and b=32
There fore T(
0
F) = 1.8(T
0
C) + 32
0
C 0 1 2 3 4 5
K
273
274 275 276 277 278
0
C
0
1 2 3 4 5 6 7 8 9
0
R 493 494 495 496 497 498 499 500 501
285 mm Hg 101.325 kPa
760 mmHg
15
492
Note that a degree is both a temperature and a temperature interval. Consider the temperature
interval from 0
0
C to 5
0
C. There are 9 Fahrenheit and 9 Rankine degrees in this interval. And only 5-
Celsius degrees and 5 Kelvin. An interval of 1 degree Celsius or Kelvin therefore contains 1.8 F or
Rankine degrees.

0
C
=1.8

0
C = 1.8
0
F
and
K = 1.8 or K = 1.8

0
R

0
R
0
R
1.8 Convert:
Dimensional Consistency. The Van der Waals equation, p+(a/V
2
)(V-b)=RT, shows that the constant
a must have the units (pressure)(volume)
2
in order that for the expression in the parentheses to be
consistent throughout. If the units of pressure are atm and those of volume are cm
3
, a will have the
units specifically of (atm)(cm)
6
. Similarly, b must have the same units as V, cm
3
. T is in K, the units
of R is (cm)
3
(atm)/(g-mol)(K). Therefore all equations must exhibit dimensional consistency.
1.9A microchip etching follows the relation, d= 16.2 16.2 e
0.021t
where t<200. Where d,
depth of etching in microns, (micrometer = m) t, time of etching in seconds.
What are the units associated with the numbers 16.2 and 0.021? Convert the relation so
that d can be expressed in inches and t can be minutes.
Both the values of 16.2 must have the units of microns. The exponential must be dimensionless so
that 0.021 must have the units of 1/seconds.
= 6.38x10
-4
(1-e
1 - 1.26 t min
)
1.103Conversion of equations The heat transfer equation is given by
Convert C
P,
heat capacity, Btu/lb
0
F to kCal/kg
0
C
D, Diameter of pipe, inch to m
G, Mass velocity, lb/ft
2
s tokg/m
2
s
0
C
0
F K
0
R
-40 --- --- ---
--- --- 77 ---
--- --- --- 698
--- 69.8 --- ---
16

'

min
m 1.0
s 60 21 . 0
6
6
exp 1
0 . 1
inch 37 . 39
10
0 . 1 10 2 . 16
t
s
m
m m x
d
2 . 0
8 . 0
2 . 0
8 . 0
6 . 16
D
G C
D
G C
h
p p


h, heat transfer co efficient, Btu/hr ft
2

0
C to kCal/m
2
hr
0
C
h = h
Btu
252
Cal
1 kCal 1 ft
2
1.8
0
F
=
(4.88)
h
hr ft
2
o
F
1Btu
1000
Cal
(0.3048m)
2
1 K
C
p
= C
p
Btu
252
Cal
1kCal 1 lb
1000
g
1.8
0
F
=
0.999
Cp
lb
0
F
1
Btu
1000
Cal
454
g
1 kg 1 K

1.11 Vapor pressure of benzene in the temp. range of 7.5
0
C to 104
0
C is calculated by Log
10
p= 6.9057 1211.0) / (t + 220.8),
where p is vapor pressure, torr(mm Hg), T is temperature in
0
C. Convert the above
equation in to SI units.
1.10 According to Archimedes principle, the mass of a floating object equals the mass of the
fluid displaced by the object. Use this principle to solve,
A wooden cylinder 30.0 cm high floats vertically in a tub of water (density = 1.0 g/cc). The
top of the cylinder is 14.1 cm above the surface of the liquid.
a. What is the density of the wood?
b. The same cylinder floats vertically in a liquid of unknown density. The top of the
cylinder is 20.7 cm above the surface of the liquid. What is the liquid density?
17
2 . 0
2 . 0
2 . 0
8 . 0 '
8 . 0
2 2
2
2
8 . 0
' 8299 . 0
inch 2 1
m 3048 . 0 inch 1
'
2813 . 0
0.3048
ft 1
g 1000
kg 1
lb 1
g 454
'
D D D
G
m s ft
lb
G G

'

'

2 . 0 '
8 . 0 '
'
48 . 0
558 . 3 )( Cp 999 . 0 ( 6 . 16
.88 4
D
G
h
47 . 0
023 . 0
2 . 0
33 . 0 67 . 0 8 . 0
D
C k G
h
p
i

1.11 An empirical equation for calculating the inside heat transfer coefficient, h
i
, for the
turbulent flow of liquids in a pipe is given by:
where h
i
= heat transfer coefficient, Btu/(hr)(ft)2 F)
G = mass velocity of the liquid, lbm/(hr)(ft)2
k = thermal conductivity of the liquid, Btu/(hr)(ft)(F)
Cp = heat capacity of the liquid, Btu/(lbm)(F)
= Viscosity of the liquid, lbm/(ft)(hr)
D = inside diameter of the pipe, (ft)
a. Verify if the equation is dimensionally consistent.
b. What will be the value of the constant, given as 0.023, if all the variables in the equation are
inserted in SI units and h
i
is in SI units?


lb
m
.ft/s
2
1 N = 1 kg.m/s, 1 lb
f
= 32.174 lb
m
. ft/s
2
and g
c
= 32.174

1 lb
f
ft 1 lb
f

If mass is 62.4 lb
m
, then weight is (62.4) (g/g
c
) = 62.4 lb
m

S
2

32.174 lb
m
. ft/s
2

1.14 The density of a fluid is given by = 70.5 exp (8.27 x 10
-7
P)
where is density (lb
m
/

ft
3
) and P is pressure (lb
f
/ in
2
)
i. What are the units of 70.5 and 8.27 x 10
-7
ii. Calculate the density in g /cc for a pressure of 9.00 x 10
6
N/m
2
iii. Derive the formula for , g/cc as a function of P(N/m
2
). Check answer using the solution of
part (ii)
Solution:
i) 70.5 lb
m
/ft
3
and8.27 x 10
-7
in
2
/lb
f
ii.

=
70.5
lb
m
exp
8.27 x 10
-7
in
2
9 x 10
6
N 14.496 lb
f
/in
2
ft
3
lb
f
m
2
1.013 x 10
6
N/m
2
18
19
constant this of value on the effect any
have not will parameters of units in change a ess dimensionl is 0.023 b.
consistant lly dimensiona is equation The
F ft hr
Btu
0.023 h
hr hr
hr

F F
1

ft ft ft
ft

lb lb
lb Btu 0.023
units like all group Next
hr ft
lb
ft
F lb
Btu
F ft hr
Btu
hr ft
lb
023 . 0
0 0.2
i
67 . 0 8 . 0
0.47
33 . 0 0 67 . 0 0 2 . 0 67 . 0 6 . 1
47 . 0
47 . 0
m
33 . 0
m
8 . 0
m
0.67
47 . 0
m 2 . 0
33 . 0
0
m
67 . 0
0
8 . 0
2
m

,
_

,
_

,
_

,
_

= 70.5
lb
m
35.3145
ft
3
1 m
3
1000 g
=1.13
g/cc ft
3
m
3
2.2
lb
m
lb
m
35.3145 ft
3
1 m
3
1000 g
= 70.5
ft
3
m
3
10
6
2.2 lb
m
lb
m
g 1 lb
m
28317 cm
3
= = 62.43
ft
3
cm
3
453.593 g 1 ft
3
lb
f
N 0.2248 lb
f
1 m
2
P = P = 1.45 x10
-4
P
in
2
m
2
1 N 39.37
2
in
2

62.43 = 70.5 exp( 8.27 x10
-7
)(1.45 x 10
-4
P)
= 1.13 exp 1.2 x 10
-10
P
therefore at P = 9 x 10
6
N/m
2
,

= 1.13 exp (1.2 x 10
10
) (9 x 10
6
) 1.13 g/cc
1.15 Check for dimensional homogeneity the equation
P = 14 L / D
2
Where P pressure drop lb
f
/ft
2
L pipe length ft
fluid velocity ft/s
fluid viscosity lb
m
/ ft-s
D pipe diameter ft
If units are not consistent what factor must be added to the right hand side of the equation to
provide consistency.
We have for both sides, (M L T
2
) /L
2
= L (LT
-1
) (ML
-1
T
-1
)(L
-2
)
ML
-1
T
-2
= ML
-1
T
-2
Therefore the equation is dimensionally homogeneous.
But if units are written for both sides then,
lb
f
ft ft lb
m
1
= = lb
m
/ ft-s
2
20
ft
2
s ft.s ft
2
The equation is not consistent dimensionally. To make it consistent then
lb
f
ft-s
2
lb
m
ft-s
2
= 1.0
ft
2
lb
m
ft s
2
lb
m
LHS term becomes, lb
f
s
2
x = (1/g
c
) units
lb
m
ft
Hence RHS is to be multiplied by (1/g
c)
1.16. The variation of thermal conductivity of a metal with temperature is often correlated
using an expression of the form k=k
o
+ aT, where k is the thermal conductivity and T
is the temperature in K. The units of a in SI system will be
GATE 1998
(a) W/mK (b) W/m (c) W/mK
2
(d) none, a is just a number
1.17 Liquid mixture is prepared by combining N different liquids with densities
1,

2,.

N.
The volume of component i added to the mixture is V
I
and the mass fraction of this
component in the mixture is x
i
. The components are completely miscible.
Determine which of the following two formulas should be used to estimate the density of the
liquid mixture,
ave,
if the volume of the mixture equals the sum of the pure component
volumes.
Determine whether (A) or (B) is correct formula (show your proof), and then use correct
formula to estimate the density (g/cc) of a liquid mixture containing 60 wt% acetone, 25 wt
% acetic acid, and 15 wt% carbon tetra chloride.
We have,
x
i
= m
i
/M
i
= m
i
/ V
i

ave
= M/V
1.17 Many liters of liquid A (density 1.4 g/cc) are to be mixed with 10 liter of liquid B (density
1.18 g/cc, so that the resultant mixture will have a density of 1.2 g/cc? Neglect the
volume change due to mixing.

Equivalent weight of an element or compound is defined as the ratio of the atomic weight or
molecular weight to its valence.
21



N
i i
i
N
i
i x ave
B
x
A x
1 1 ave
) ...( ..........
1
and ) ........(


g/cc 917 . 0 or 091 . 1
595 . 1
15 . 0
049 . 1
25 . 0
791 . 0
60 . 0 1
correct
1 1
:
useful not
1
:
2
+ +

ave
i
i
ave
ave
i
i
i i
i
i
ave
i
i
i
i i
i i
x
M
V
V
M m
V
M
m x
B
V
m
M V
m
M
m
x A

Molecular weight
Equivalent weight =
Valence
The concentration of solution can be expressed in terms of normality, molarity, and molality.
Normality (N) is the number of g-equivalents of solute dissolved in one liter of solution.
g-equivalents of solute
Normality =
Volume of solution (L)
Concentration, g/cc = (N) (Eq,wt)
Molarity (M) is the number of g-moles of solute dissolved in one liter of solution
g-moles of solute
Molarity =
Volume of solution (L)
Molality is the g mole of the solute dissolved in one kg of solvent
g- mole of solute
Molality =
Mass of solvent in kg
Equivalent weights of
HCl = 36.5 NaOH = 40 Na
2
CO
3
= 53 H
2
SO
4
= 49
H
3
PO
4
= 32.67 CaCl
2
=111 FeCl
3
=54.17 KMnO
4
=31.6
1.18 The Concentration of SO
2
in the flue gas from a boiler is found to be 0.2 kg/m
3
at NTP.
Determine the concentration of SO
2
in ppm by volume at NTP. Assume that the gases
are perfect. GATE 92
Basis: 1.0 m
3
of flue gas at NTP
SO
2
in flue gas = (0.2/64) 22.4 = 0.07 m
3
at NTP
In ppm = 0.07 (10
6
) = 70000 ppm
2. Method of expressing Chemical composition
In stoichiometric calculations, the mass relations existing between the reactants and products of a
chemical reaction are of primary interest. To get these informations the following procedures are
adopted
1. Write the balances reaction equation.
2. Find the atomic / molecular weights of all elements /molecules involved in the reaction

From this it is possible to calculate the mass of a particular component required or product produced
in a given problem.
MASS, VOLUME RELATIONS: One gram mole of any substance will occupy 22.414 liter at
NTP or 1 kg mole will occupy 22.414 m
3
22
Mole = (weight of substance / molecular weight)
g mole = ( g of substance / molecular weight) and kg mole = kg of substance / mol.wt.
2.1 For the reaction between BaCl
2
+ Na
2
SO
4
2NaCl +BaSO
4

i. How many grams BaCl
2
will be required to react with 5 g of Na
2
SO
4
?
ii. How many grams of Na
2
SO
4
have been added to BaCl
2
if 5g of BaSO
4
is precipitated.
Solution BaCl
2
+ Na
2
SO
4
2NaCl + BaSO
4
208.36 142 117 233.36
Basis: 1. 5g Na
2
SO
4

142 g Na
2
SO
4
requires 208.36 g BaCl
2
5g Na
2
SO
4
requires (208.36)(5) / (142) = 7.336g
2. 5g BaSO
4

233.6 g BaSO
4
needs 142 g Na
2
SO
4
5 g BaSO
4
requires (5)(142) / (233.6) = 3.04g
2.2 How much charcoal is required to reduce 1.5 kg arsenic trioxide (As
2
O
3
)
a) How much of CO is produced per kg charcoal.
As
2
O
3
+ 3C 3CO + 2 As
197.8

36 84 149.8
Basis: a) 1.5 kg As
2
O
3
1.5 kg As
2
O
3
36 kg Carbon
= 0.27 kg Charcoal
197.8 kg As
2
O
3
b) 1 kg Charcoal
1 kg Charcoal 84 kg CO
= 2.33 kg CO
36 kg Charcoal
2.3 Production of SO
2
Cu + 2H
2
SO
4
CuSO
4
+ 2H
2
O + SO
2
63.54

196 159.54 36 64
a) How many grams Cu?
b) And how many grams 94% H
2
SO
4
must be heated to get 32 kg SO
2

Basis: 32kg SO
2

a) 32 kg SO
2
63.54 kg Cu
= 31.77 kg Cu
64 kg SO
2

b) 32 kg SO
2
196 kg H
2
SO
4

= 98 kg H
2
SO
4
(100%)
64 kg SO
2
= (98 / 0.94) = 104.26 kg H
2
SO
4
23
2.4 The burning of lime stone CaCO
3
-----> CaO + CO
2
goes only 70% completion in a kiln.
a) what is the mass% of solids withdrawn? b) how many kg of CO
2
is produced per kg
lime stone?

Basis: 100 kg mol CaCO
3
fed to kiln, 70 % reacts
70 kg mol CaO 57 kg CaO
= 3990 kg CaO
1 kg mol CaO
70 kg mol CO
2
44 kg CO
2
= 3080 kg CO
2
kg mol CO
2

30 kg mol CaCO
3
101 kg CaCO
3
= 3030 kg CaCO
3
1 kg mol CaCO
3
170 kg mol total. Solid mass = 3990 + 3030 = 7020 kg
moles= 70 + 30 = 100
a) CaO = (3990 / 7020)= 56.8% b) CaCO
3
= (3030 / 7020) = 43.2%
2.5 Lime stone analysis: Calcium carbonate = 94.52% , Mg.Carbonate = 4.16%, insoluble
matter = 1.32%
a) How many kg calcium oxide could be added from 4Ton lime stone
b) How many kg CO
2
is given out per kg limestone.
CaCO
3
CaO + CO
2
MgCO
3
MgO + CO
2
a) Basis: 4000kg limestone.
kg CaCO
3
present in limestone = (4000) (0.9452) = 3780.8 kg
kg MgCO
3
in limestone. = (4000)(0.0416) = 166.4kg
3780.8 kg CaCO
3
56 kg CaO
= 2117.25 kg CaO
100 kg CaCO
3
b. 4000kg Limestone
3780.8 kg CaCO
3
44 kg CO
2
166.4 kg MgCO
3
44 kg CO
2
+
100 kg CaCO
3
84.3 kg MgCO
3
= 1750.383 kg CO
2
= (1750.383 / 4000) = 0.4376 kg CO
2
per kg limestone
2.5 Sulfuric acid can be manufactured by contact process according to,
i. S + O
2
SO
2
ii. 2SO
2
+ O
2
3SO
3
iii. SO
3
+ H
2
O H
2
SO
4
24
u r asked as part of the preliminary design of a sulfuric acid plant with a design capacity
of 2000 ton/day (93.2% H
2
SO
4
by weight

)to calculate the following
a. how many tons of pure sulfur are required per day to run the plant?
b. how many tons of oxygen are required per day?
c. how many tons of water are required per day for the reaction (iii) ?
Basis: 2000 ton 93.2% H
2
SO
4
per day
a. 2000 ton soln. 0.932 ton H
2
SO
4
1 ton mole H
2
SO
4
1 ton mol S 32 ton S
= 609 ton S
1 ton soln. 98 ton H
2
SO
4
1 ton mol H
2
SO
4
1 ton mol S
609 ton S 1 ton mol S 1.5 mol O
2
32 ton O
2
b = 913.5 ton O
2
32 ton S 1mol S 1 ton mol O
2


609 ton S 1 ton mol S 1 mol H
2O
18 ton H
2
O
c = 342.6 ton H
2
O
32 ton S 1mol S 1 ton mol H
2
O
2.7 Find the nitrogen content of 100 kg urea sample containing 96.43% urea.
Basis: 100 kg urea. [ NH
2
CONH
2
]
96.43 kg urea 28 kg Nitrogen
= 45 kg Nitrogen
60 kg urea
2.8 Gaseous propane, C
3
H
8,
is to be liquefied for storage in steel cylinders. How many grams
liquid propane will be formed by the liquefaction of 500L of gas, the volume being
measured at STP?
Basis: 500L C
3
H
8
at STP 500 L 1 g mole
= 22.307 g mole
22.414 L

Wt of C
3
H
8
= (g.mole )( mol.Wt) = (22.307) (44) = 981.5 g
2.9 If 45g Fe react, Fe + H
2
SO
4
FeSO
4
+ H
2


55.8

98

151.8 2

How many Liters of Hydrogen gas are liberated at STP?
Basis: 45 g Fe = 45 / 55.8 = 0.806 g.mole Fe
0.806 g.mole Fe 1 g.mole H
2
22.414 L
=18.066 L
1 g.mole Fe 1 g.mole H
2
25
2.10 The gas acetylene is formed by
CaC
2
+ 2H
2
O C
2
H
2
+ Ca(OH)
2
64 36

26 74
Calculate the no. of hours of service that can be derived from one kg carbide in an
acetylene lamp, burning 1.5m
3
of gas per hour at STP?
Basis: 1 kg CaC
2
1 kg CaC
2
26 kg C
2
H
2

= 0.406 kg = 0.406 / 26 = 0.01562 kg mole C
2
H
2
64 kg CaC
2
0.01562 kg mole C
2
H
2
22.214 m
3
= 0.35 m
3

1 kg mole C
2
H
2
0.35 m
3
C
2
H
2
1 hr
= 0.233 hr = 14 min
1.5 m
3
C
2
H
2
3. Methods of expressing composition of mixtures and solutions:
System with more than two components can be expressed in wt% , vol% and mole% etc., The
composition of solid systems and liquid systems is expressed in terms of wt% and also in terms of
mole%. The composition of gasses is expressed in terms of vol%.
Weight %: Weight of A
Wt% of A = . 100 or (weight fraction of A) x 100
Total Wt of system
= (W
A
/ W
T
) X 100
where W
T
The weight of the system given by W
A
+ W
B
+ .
Volume %:
Vol% of A = (V
A
/ V
T
) X 100 or (vol fraction of A) x 100
where V
T
Total Vol of the system
Mole %:
Mole of A
Mole% of A = X 100 or (mole fraction of A) X 100
Total moles of system
Parts per million & Parts per billion: (ppm & ppb) are used to
express the concentrations of trace species in the mixture of gasses or
liquids. If y
i
is the fraction of component i, then ppm
i
= y
i
x10
6
and ppb
i
=
y
i
x 10
9
Shown at the right is a cartoon depicting the molecules in a VLE
system. Note that the composition of blue molecules in the vapor phase is
26
given by (number of full circle) / (number of full circles + number of empty circles), or y = 3/5 =
0.6. Similarly, the mole fraction of full circles molecules in the liquid phase is given by x = 8/20 =
0.4.
3.1 A liquid that is almost entirely H
2
O is reported to contain 125 ppb phenol (mass basis)
i) What is the mass fraction of phenol in the liquid?
ii) How many mg of phenol are contained in 1kg of liquid?
iii) What is the approximate conc. of phenol in the liquid in g/l ?
3.2 An aqueous solution of NaCl is prepared by dissolving 25 kg NaCl in 100 kg H
2
O. Find
the wt% and mole% of composition of solution.
Basis: 25kg NaCl and 100kg H
2
O
Total wt of solution is 100+25 = 125 kg
Wt% on NaCl = (kg NaCl / kg solution) x 100 = 25 v 100 / 125 = 20
Wt% of H
2
O = (kg H
2
O / kg solution ) x 100 = 100 x 100 / 125 = 80
Mol wt. Of NaCl = 58.5, Moles of NaCl = 25 / 58.5 = 0.427 moles
Mol Wt. Of H
2
O = 18, Moles of H
2
O = 100 / 18 = 5.56 moles
0.427
Mol % of NaCl = x 100 = 7.13
0.427 + 5.56
5.56
Mol% H
2
O = x 100 = 92.87
0.427 + 5.56
(Test Q: ) Ethanol and H
2
O form a azeotrope containing 96% (by wt) ethanol. Find the
composition of azeotrope by mole%.
Hint: 100kg azeotrope
(Test Q: ) Nitric acid and water form a azeotrope containing 62.2 mole% water. Find the
composition of azeotrope by wt%.
Hint: 100kg mole azeotrope
3.2 An aqueous solution contains 15% ethanol by volume. Find the wt percent of ethanol if

ethanol
and
water
are 0.79 and 1.0 g/cm
3
.
Basis: 100cm
3
aqueous soln.
100 cm
3
aq. Soln 15 cm
3
ethanol 0.79 g ethanol
= 11.85 g ethanol
100 cm
3
aq.soln. 1 cm
3
ethanol
100 cm
3
aq. Soln 85 cm
3
H
2
O 1 g H
2
O
100 cm
3
aq. Soln 1 cm
3
H
2
O = 85 g H
2
O
11.85
wt% of ethanol = x 100 = 12.23%
27
11.85 + 85
3.4 The available nitrogen (N) in the urea sample is 45% by wt. Find the actual urea content in
the sample.
Hint: 100 kg (Urea)
impure
sample [ NH
2
CONH
2
]
100 kg (Urea)
impure
5 kg N
2
60 kg (Urea)
pure
96.428 kg (Urea)
pure
=
100 kg (Urea)
impure
28 kg N
2
100 kg (Urea)
impure
3.5 The nitrogen content of NH
4
NO
3
sample is given as 34.5%. Find the actual ammonium
nitrate content of the sample?
Basis: 100 kg sample mole Wt of NH
4
NO
3
= 80
Actual impure amount of N
2
= 34.5 80kg pure nitrate
= 98.57 kg
28kg nitrogen
Actual pure nitrate in 100 kg sample is 98.57 kg.
3.6 Spent acid from a fertilizer plant has following compositions by wt.
H
2
SO
4
20%, NH
4
HSO
4
45%, H
2
O30% and remaining organic compounds. Calculate
the total acid content of spent acid in terms of H
2
SO
4
after adding the acid content
chemically bound in NH
4
HSO
4
.
NH
3
+ H
2
SO
4
--- NH
4
HSO
4
Basis: 100kg spent acid. MW of NH
4
HSO
4
= 115, H
2
SO
4
= 98
1 mole of NH
4
HSO
4
= 1 mole of H
2
SO
4
.
115kg of NH
4
HSO
4
= 98kg H
2
SO
4
In spent acid, NH
4
HSO
4
, 45 kg 98 kg H
2
SO
4
= 38.35 kg H
2
SO
4
in
115 kg NH
4
HSO
4
NH
4
HSO
4
Chemically H
2
SO
4
available = 38.35 kg.
Total H
2
SO
4
= 20 + 38.35 = 58.35kg in spent acid.
3.7 How much super phosphate fertiliser can be made from one tonne of calciumphosphate,
93.5% pure?
Ca
3
(PO
4
)
2
+ 2 H
2
SO
4
CaH
4
(PO
4
)
2
+ 2 CaSO
4
3.8 What will be the percentage Na
2
O content of the lye containing 73% caustic soda?
Basis: 100 kg lye
2NaOH Na
2
O + H
2
O


2 X 40

62 18
lye contains 73 kg NaOH 62 kg Na
2
O
= 65.575 kg Na
2
O
80 kg NaOH
3.9 Caustic soda flakes obtained from a manufacturer are found to contain 60ppm silica
(SiO
2
). What is the percentage impurity by weight.
28
Basis: 10
6
kg Caustic Soda Flakes
60kg silica
(100) = 0.006
Amount of flakes 10
6
kg
3.10 If the components of air are N
2
78%,

O
2
21%, Ar 0.9% and CO
2
0.1% by volume, what is
its MW ?
78(28) + 21 (32) + 9 (40) +1 (44)
MW wt. of air = = 28.964 g / g mol
78 + 21 + 9 + 1
3.11 The molar composition of a gas is 10% H
2
, 10% O
2
, 30% CO
2
and balance H
2
O. If 50%
H
2
O condenses, the final mole percent of H
2
in the gas on a dry basis will be
GATE 2000
(a) 10% (b)5% (c)18.18% (d) 20%
On dry gas basis, it does not matter how much water condenses.
% 20
30 10 10
100 10
H %
2

+ +

3.12. A solution of specific gravity 1.0 consists of 35% A by weight and the remaining B. If the
specific gravity of A is 0.7, the specific gravity of B is
GATE 99
(a) 1.25 (b) 1.3 (c) 1.35 (d) 1.2
3 . 1
65 . 0
7 . 0
035 . 0
1
1
B
B

4. IDEAL GAS LAW

Boyles law: PV = constant combining both PV/T = constant =R
Charls law: V / T = constant Where R is universal gas constant
Therefore PV = RT.

IF there are n no. of moles, PV = nRT
At two different conditions P
1
V
1
= nRT
1,
P
2
V
2
= nRT
2
OR, P
1
V
1
/ T
1
= P
2
V
2
/ T
2
Volume occupied at 0
o
C and 101.325 kPa (1 atm) by 1kmole gas = 22.4136 m
3
Gaseous mixtures: In case of gas mixtures contained in a closed vessel the molecules of each
component gas distributed throughout the entire volume. The total pressure exerted by the
mixture is equal to the sum of pressures exerted by each individual component gas.
Partial pressure is the pressure in the mixture of gases that would be exerted by that component gas
if it were present in the same volume and temperature.
DALTON LAW:
29
The total pressure exerted by a gaseous mixture is equal to the sum of partial pressures of
component gasses.
P = P
A
+ P
B
+ P
C
+ --------------
AMAGATS LAW:
The total volume occupied by a gaseous mixture is equal to the sum of pure component
volumes.
V = V
A
+

V
B
+ V
C
+ ---------------
Relationship between partial pressure, mole fraction of component gas to total pressure:
Volume % = Mole % = Pressure %
V= v
a
+v
b
+ v
c
+ . And P = p
a
+ p
b
+.
From ideal gas law we have (p
a
V) = n
a
RT or p
a
= (n
a
RT) / V (1)
p
b
= (n
b
RT) / V
p
c
= (n
c
RT) / V
then P = p
a
+ p
b
+p
c
+.= {(RT) /V}(n
a
+ n
b
+ n
c
+ .) (2)
p
a
n
a
Dividing (1) / (2), =
p
a
+ p
b
+ p
c
+ n
a
+ n
b
+ n
c
+ .
p
a
n
a
. 100 = .100
p
a
+ p
b
+p
c
+ n
a
+ n
b
+ n
c
+ .
Pressure % = mole % for gases that are ideal.
Similarly, we have P v
a
= n
a
RT ..(3)
P v
b
= n
b
RT
P v
c
= n
c
RT
Adding,
P(v
a
+ v
b
+ v
c
+ ) = RT (n
a
+ n
b
+ n
c
+) .(4)

Dividing equation (3) by (4)
v
a
n
a
X 100 = X 100
(v
a
+ v
b
+ v
c
+ ) (n
a
+ n
b
+ n
c
+)
volume % = pressure % = mole %
Average molecular wt. Of gas mixture: Here it is assumed that the quantity of gas mixture has one
mole as the weight of one mole of gas mixture represents its average molecular weight.
Let M
A
, M
B
, M
C,
so on and X
A
, X
B
, X
C
so on, are the molecular weights and mole fractions of
component gasses and MW
ave
is average molecular weight, then
MW
avg
= M
A
X
A
+ M
B
X
B
+ M
C
X
C
+ ---------- and 1 / (MW)
ave
= [y
1
/ (MW)
1
] + [y
2
/(MW)
2
]
+ .
30
Where y
1
,y
2
, are weight fractions.
Density of gas mixture :
We have PV = nRT, P / RT = n / V
where n moles of gas mixture
V m
3
of gas mixture
R 8.31451 m
3
kPa / kmole K
T K
P atm
But n, moles of gas mixture = (kg of gas mixture) / MW
ave
P / RT = [ weight of gas mixture / MW
ave
] X [ 1 / V ]
= [ weight of gas mixture / Volume ] X [ 1 / MW
ave
]
(P MW
ave
)

/ RT =
mix
= kg / m
3
4.1 Ideal gas law is applicable at GATE 94
(a) low T, low P (b) high T, high P (c) low T, high P (d) high T, low P.
4.2 Assuming that CO
2
obeys perfect gas law, calculate the density of CO
2
(in kg/m
3
) at
263
o
C and 2 atm. GATE 95

(a) 1 (b) 2 (c) 3 (d) 4
= PM/RT = (2 x 44 x 1000)/(82.06 x 236.15) = 2
4.3 Find the volume of CO
2
at 25
o
C and 750mm Hg if volume of CO
2
is 15m
3
at 760mm and
20
o
C ?
V
1
= 15m
3
T
1
= 20 + 273 = 294K P
1
= 760mm Hg
V
2
= ? T
2
= 25 + 273 = 298K P
2
= 750mm Hg
V
2
= V
1
(T
2
/ T
1
) (P
1
/ P
2
) = V
1
(Temp correction) (Pressure correction)
V
2
= 15 (298 / 293) (760 / 750)
V
2
= 15.4594m
3
The ratio of temperature or pressure corrections should be greater than unity when the
changes in pressure or temperature, are to cause the increase in volume. The ratio should be less than
unity when the changes are to cause decrease in volume.
4.4 A product gas from a reaction has the composition by weight.
Cl
2
67%, Br
2
28%, O
2
5%, using the ideal gas law calculate
a) the composition of gas by volume
b) the density of the mixture in g/L at 25
o
C
c) Specific gravity of the mixture.
d) Average molecular weight of the mixture.
Basis: 100g of product gas
31
Component Weight
Molecular
weight
Mole Mole %
Cl
2
67 71 0.944 74.04
Br
2
28 160 0.175 13.72
O
2
5 32 0.156 12.24
Total 100 1.275 100
Volume of the mixture at 25
0
C, (1.275)(22.414)(298/273) =31.195 L
100 g
Density of the mixture at 25
0
C = = 3.23 g/L
31.195 L

density of mixture 3.23
Specific gravity of mixture = = = 2.726
density of air 1.185
Total weight of mixture 100
Average molecular weight = = = 78.43 g / g mole
Total moles of mixture 1.275
4.5 A mixture of gases is analyzed and found to have the following composition:
CO
2
12.0%, CH
4
27.3, H
2
9.9, N
2
44.8, and CO 6.0
How much will 3 lb moles of this gas mixture weight?
4.6 A gas mixture is found to contain the following composition by volume. Ethylene 30.6%,
benzene 24.5%, oxygen1.3 %, ethane 25%, nitrogen 3.1%.

Find i. Composition in mole %
ii. Weight %
iii. Average molecular weight of gas sample
iv. Density of gas at NTP
Basis: 100 mole gas mixture
Component Mole Molecular Weight Weight %
C
2
H
4
30.6 28 856.8 22
C
6
H
6
24.5 78 1911.0 49.07
O
2
1.3 32 41.6 1.07
CH
4
15.5 16 248 6.37
C
2
H
6
25 30 750 19.26
N
2
3.1 28 86.8 2.23
Total 100 3894.2 100
Average molecular weight =( Total weight) / Total moles) = (3894.2 /100) = 38.942 g / mole
Density at NTP = (total weight / volume ) = 3894.2 /(100 x 22.414) =1.737 g/L
4.7 A compound whose molecular weight is 103, analyses C81.5%, H
2
4.9% and N
2

13.6%. What is its molecular formula?

Hint: g atom of element = weight in gram / atomic weight
Basis: 103kg of compound.
i) Weight of carbon; 103kg compound 81.3kg C
= 83.95 kg C
100kg compound
32
Atoms of C = 83.95 / 12 = 6.99 = 7
ii) Weight of hydrogen; 103kg compound 4.9kg H
2
= 5.05 kg H
2
100kg Compound
Atoms of Hydrogen = 5.05 / 1 = 5
iii) Weight of Nitrogen; 103kg compound 13.61 N
2
= 14.01 kg
100kg Compound

Atoms of Nitrogen = 14.01 / 14 = 1
Molecular formula is C
7
H
5
N
4.8 Derive the empirical formula of the following: Ag 9.09%, N 20.77, O 70.13%
4.9 A solid compound is found to contain 42.11% Carbon, 51.46% Oxygen, 6.43%
Hydrogen. Its molecular weight is about 341. what is the formula of the compound.
4.10 How many ppb are there in 1 ppm?
4.11 A gas mixture consists of 3 components A, B & C. The following is the analysis of this gas
mixture.
A 40 mole % ---------- mol.Wt = 40
B ---------- 18.75 wt% mol.Wt = ?
C 20 mole % ---------- mol.Wt = 50
Calculate a) MW of B
b) Ave. MW of mixture
sol:
Basis: 100kg mole of mixture
MW Mole% Weight%
A 40 40 ----------
B X 40 18.75
C 50 20 ----------
100 100
40(X)
a) wt% of B = 18.75 = . 100
(40)( 40) + 40(X)+ (50 X 20)
by solving the above we get X = 15
b) Average MW = (MW.X )
A
+ (MW.X)
B
+ (MW.X)
C
= (40)(0.4) + (15)(0.4) + (50)(0.2) = 32
4.11 A mixture of CH
4
& C
2
H
6
has MW
ave
of 22.4. Find the mole% of CH
4
& C
2
H
6
in the
mixture.
33
MW
ave
= MW
CH4
(X)
CH4
+ MW
C2H6
(X)
C2H6
22.4 = 16 (X)
CH4
+ 30 (X)
C2H6
, But (X)
C2H6
+ (X)
CH4
=1

then (X)
CH4
=0.543 and (X)
C2H6
= 0.457
4.12 Two different engineers calculate the average molecular weight of a flue gas sample.
One engineer uses correct mass of 28 for N
2
and determines average molecular weight to
be 30.08, the other using an incorrect value of 14 calculates the average molecular
weight to be 18.74
a) Calculate the volume % of N
2
in the flue gas sample.
b) If the remaining components of the flue gasses are CO
2
and O
2
calculate the
volume percent of each of them.
a) Engineer I : 30.08 = 28.X
n
+ (M
f
. X
f
)
Or M
f
.X
f
= 30.08 28X
n
Engineer II 18.74 = 14X
n
+ (30.08 28X
n
)
X
n
= 11.24 / 14 = 0.81 OR 81%
b) It is given that the remaining 19% contains CO
2
and O
2

Then we have 30.08 = 28.X
n
+ 32 X
O2
+44 X
CO2

= 28 (0.81) + 44 X
co2
+ 32X
O2

But we have, X
CO2
+ X
o2
=0.19 OR X
CO2
= 0.19 X
O2
By solving the above, we get X
o2
= 0.08 and X
co2
= 0.11
4.13 Two engineers are calculating the average M W of gaseous mixture containing oxygen
and other gases. One of them using the correct MW of 32 for oxygen determines MW
correctly as 39.8. The other using an incorrect value of 16 determines MW as 32.8. This
is only an error in his calculations. What is the mole % of oxygen in the mixture.
Engineer I: MW
ave
=39.2 = 32.Xo
2
+ M X
g
or M X
g
= 39.2 32 Xo
2
Engineer II: MW
ave
= 32.8 = 16 Xo
2
+ {39.2 32 Xo
2
} or Xo
2
= 0.4
Substituting in engineer I equation, mole % of oxygen in the mixture = 40
4.14 Two thermometers are to be checked against standard thermometer, which are
calibrated in
0
C and K .The standard reads 22
0
F. What should the other two
thermometers read?
4.15 1000 m
3
of a mixture H
2
, N
2
and CO
2
, at 150
0
C was found to have the following ratio of
partial pressure of gases P
H2
: P
N2
: P
co2
= 1 : 4 : 3. If the total pressure is 2 atmosphere
absolute, find mole fraction , weight %, of each of these gases, MW
ave
and weight of CO
2
in kg
Basis: 1000 m
3
of mixture of gas at 150
0
C
Partial Pr. of H
2
= P
H2
= 2 (1/8) = 0.25 atm
P
N2
= 2 (4/8) = 1.0 atm.
P
co2
= 2 (3/8) = 0.75 atm.
34
No. of moles of H
2,
P
H2
V = n
H2
RT
(0.25)(1000) = n
H2
(0.8206)(273+150) or n
H2
= 7.203 kg mole
similarly n
N2
= 28.813 kg mole
n
CO2
= 21.609 kg mole
Compone
nt
Hg mole M W Weight, kg Wt % Mole
fraction /
Pr.
fraction
H
2
7.203 2.0 14.406 0.81 0.125
N
2
28.813 28.0 806.764 45.53 0.500
CO
2
21.609 44 950.796 53.66 0.375
Total 1771.996
MW
ave.
= 2 (0.125) + 28 (0.5) +44 (0375) = 30.75
Wt. of CO
2
=950.796 and density of mixture = (1771.966 / 1000) = 1.77 kg /m
3
4.16 250 cc of N
2
at 750 mm Pr. is mixed with 100 cc of H
2
at 550 mm Pr. in an an empty globe
of capacity 100 cc. What is the partial Pr. of N
2
in the mixture and the total Pr.?
4.17. A mixture of CH
4
and C
2
H
6
has density 1.0 kg/m
3
at 273 K and 101.325kPa. Calculate
the mol% and weight % of CH
4
and C
2
H
6
in the mixture
Basis: 1.0 kg/m
3
density of gas mixture at 273 K and101.325 kPa
Density of gas mixture = = PM
ave
/ RT M
ave
= (RT/P)
8.31451 (273)
M
ave
= 1.0 . = 22.4
101.325
M
ave
= M
CH4
X
CH4
+ M
C2H6
X
C2H6

22.4 = 16

X
CH4
+ 30( 1 -

X
CH4
) or X
CH4
=0.543 and X
C2H6
= 0.457
Weight of CH
4
in 1 k mol of mixture = 0.543 x 16 = 8.69 kg
Weight of C
2
H
6
in 1 k mol of mixture = 0.457 x 30 = 13.71 kg
Therefore wt % are 38.8 and 61.2
4.18 The concentration of SO
2
in the flue gases from a boiler was found to be 0.2 kg/m
3
at
NTP. Determine the concentration of SO
2
in parts per million by volume, at NTP.
Assume that the gases are perfect. Gate92
Basis: 1 m
3
at NTP flue gas
SO
2
in flue gas = 0.2 kg or (0.2/64) kg mol or (0.2/64)22.4 m
3
at NTP
Therefore SO
2
in ppm by volume = (0.2/64)22.4 m
3
x 10
6
at NTP
35
36