2014-11-23 APPCHEN Lecture Notes

DE LA SALLE UNIVERSITY Page 1
Gokongwei College of Engineering

Chemical Engineering Department
General Chemistry Calculations
(APPCHEN)
I. Basic Stoichiometric Calculations from Chemical Reactions
A. Types of Chemical Reactions
1. Combination Reaction (Synthesis) : A + B AB
a. metal + oxygen gas basic oxide or basic anhydride
2Mg + O2 2MgO
b. non-metal + oxygen gas acidic oxide or acidic anhydride
S + O2 SO2
c. non-metal oxide + water acid
CO2 + H2O H2CO3(aq)
d. metal oxide + water alkali/base
MgO + H2O Mg(OH)2
2. Decomposition : AB A + B
a. metal oxide
metal + oxygen gas
HgO
Hg + O2 (Joseph Priestley, 1774)
b. metal carbonates
metal oxide + CO2
Na2CO3
Na2O + CO2
c. metal nitrates
metal nitrites + O2
NaNO3
NaNO2 + O2
d. metal bicarbonates
metal carbonate + H2O + CO2
2NaHCO3
Na2CO3 + H2O + CO2
e. metal oxyhalides
metal halide + O2
2KBrO3 2KBr + 3O2
/ MnO2 / Fe 2 O3
3. Single Replacement : AB + C CB + A
a. Hydrogen Displacement Reactions
Na + H2O(l)NaOH + H2(g)
2Fe + 3H2O(v) Fe2O3 + 3H2(g)
Zn + 2 HCl(aq) ZnCl2 + H2(g)
b. Halogen Displacement (Activity Series : F2> Cl2> Br2> I2)
2KI + Cl2 2KCl + I2
4. Double Decomposition (Metathesis)
a. Neutralization Reaction reaction of an acid and a base forming salt and water
HCl + KOH KCl + H2O
b. Precipitation Reaction reaction which results in the formation of an insoluble product
Na2CO3(aq) + CaSO4(aq) CaCO3(s) + Na2SO4(aq)
Figure 1.Activity Series of Metals(arranged in decreasing activity)

Li K Na Ca Mg Al Mn Zn Cr Fe Ni Sn Pb H Cu Bi Sb Hg Ag Pt Au
DISPLACE HYDROGEN FROM ACIDS

DISPLACE HYDROGEN FROM STEAM
DISPLACE HYDROGEN
FROM COLD WATER
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VERGEL C. BUNGAY
De La Salle University
(APPCHEN)
Table 1.Solubility rules in water at 25C
SOLUBLE COMPOUNDS INSOLUBLE COMPOUNDS
All nitrates, bicarbonates, chlorates and compounds All carbonates, phosphates, chromates and sulfides
containing alkali metal ions and ammonium ion. except that of alkali metal ions and ammonium ion
All halides except that of Ag+, Hg22+ and Pb2+
All sulfates except that of Ag+, Ca++, Sr++, Ba++ and All hydroxides except that of alkali metal ions and Ba++
Pb++
B. Excess and Limiting Reagents

1. Stoichiometry involves quantitative relationships between reactants and products in chemical reactions
2. Limiting reactant species present in the reaction that would be completely consumed theoretically if the
reaction were to proceed to completion
3. Excess reactant reactant present in more than its stoichiometric proportion relative to every other reactant
The following quantities are computed based on the amount of limiting reactant present:
a. amount of product
b. amount of excess reactant reacted
c. amount of excess reactant left
The following methods are used to identify the limiting reactant:
a. Comparison of the amounts of reactants
b. Comparison of the amounts of products formed from each reactants
c. Evaluate the ratio, mole of reagent per stoichiometric coefficient of reagent
d.
4. Fractional excess (% excess) ratio of the amount present in excess to the amount stoichiometrically
required
n n i ,stoichiometric n i ,feed n i , theoretical
fractional excess of species, i i ,feed or
n i ,stoichiometric n i , theoretical
n i ,feed n i ,stoichiometric n i ,feed n i ,theoretical
fractional excess of species, i 100% 100%
n i ,stoichiometric n i , theoretical
5. Fractional conversion (% conversion) fraction of feed or some component in the feed that is converted to
products
n i ,initial n i ,final n n i ,final
Xi or % conversion i ,initial 100%
n i ,intial n i ,intial
C. Fractional Yield and Purity

1. Fractional Yieldratio of the amount of desired product (actual yield) to the amount product obtained if all
limiting reactant had reacted and no side reactions occurred (theoretical yield)
actual yield actual yield
fractional yield or % yield 100%
theoretical yield theoretical yield
Note:
The actual yield is usually less than the theoretical yield. In cases that the reaction goes to completion, that is,
all the limiting reactant had reacted, the actual yield is equal to the theoretical yield. At this point in the
reaction, maximum amount of product is obtained.
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VERGEL C. BUNGAY
(APPCHEN)
2. Purity amount of substance sought present in a given amount of sample

mass of substance sought
% purity 100%
mass of sample
D. Gravimetric Factor
Involves combination of the mole ratios and molar masses used in the stoichiometric calculation
Used to convert the mass of one substance in terms of the other according to a balance chemical equation
mass of substance sought
Gravimetric Factor (GF)
mass of known substance
molar mass of substance sought mole of substance sought
molar mass of known substance mole of known substance chemical reaction
Similarly, the mass of product obtained from a given amount of reactant can also be calculated using the
gravimetric factor
mass of product
mass of reactant
molar mass of product mole of product
molar mass of reactant mole of reactant chemical reaction
E. Calculations Involving Multiple Reactions
Types of multiple reactions
1. Parallel reactions or competing reactions -reactions where the reactant is consumed by two different reaction
pathways to form different products
C2H4 + H2O C2H5OH C6H6 + Cl2 C6H5Cl + HCl
2 C2H4 + H2O (C2H5)2O C6H6 + 3 Cl2 C6H6Cl6
2. Series reactions or consecutive reactions reactions where the reactant forms an intermediate product which
reacts further to form another product
C6H6 + 2 H2C6H10 + H2 C6H12
(CH2)2O CH3CHO CO +CH4
II. Properties of Solutions

A. Solution
A homogeneous mixture of two or more substances in which the substance present in lesser quantity is called the
solute whilethe substance present in greater quantity is called the solvent
1. Solution process
A solution is formed when one substance disperses uniformly throughout another
In the case of a gas dissolved in another gas, the interactions are said to be negligible and therefore
considered as a mixture rather than a solution
However, dilute gases may be considered as a solution
In general, a solution is formed when the solute-solvent interactions are greater compared to the solute-
solute interactions and the solvent-solvent interactions
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VERGEL C. BUNGAY
(APPCHEN)
2. Intermolecular forces of attraction
Ion-dipole forces
Exist between an ion and the partial charge on one end of a polar molecule
Positive ions are attracted to the negative end of the dipole and the negative ions are attached to the
positive end of the dipole
Commonly encountered in solutions of ionic substances in polar solvents
This type of force is weaker compared to the electrostatic attraction between charged particles in an
ionic compound
Dipole-dipole forces
Exist between two polar molecules
Effective only when the polar molecules are very close to each other
The molecules must be able to get near each other in the correct orientation for dipole-dipole forces
to be effective
London dispersion forces
Introduced by Fritz Wolfgang London (1900-1954)
Exist between two non-polar molecules
The motion of electrons at any given instant can provide the atom an instantaneous dipole moment
These momentary dipoles on one atom can induce a similar dipole on adjacent atoms causing an
attraction
Hydrogen bonding
A special type of intermolecular attraction exists between the bonding between hydrogen and
electronegative atoms like nitrogen, oxygen and fluorine is called hydrogen bonding
It may be considered as a special form of dipole-dipole attractions due to the large difference in
electronegativity between the hydrogen bond and the electronegative atom
Without the inner core of electrons of a hydrogen atom, the positive side of the bond dipole has its
proton barely exposed to the negative charge of the neighboring electronegative atom
3. Ionic compounds in water
When an ionic compound is added to water, the water molecules orient themselves on the surface of the
ionic crystals with the positive end of water oriented toward the anions and the positive end toward the
cations
The ion-dipole attractions are strong enough to pull the ions from their positions in the crystal
Once separated, the ions are surrounded by the water molecules which stabilize the ions in solution and
prevents the cations and anion from recombining
4. Molecular compounds in water
Dissolution of molecular compounds in water involves uniform dispersion of intact molecules
throughout the solution
Unlike ionic compounds in water, molecular compounds are being held by dipole-dipole forces
specifically hydrogen bonding
Molecular compounds which are not capable of hydrogen bonding do not dissolve in water
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VERGEL C. BUNGAY
(APPCHEN)
Figure 2. Ionic and molecular compounds in water

(http://wps.prenhall.com/wps/media/objects/140/143401/GIFS/AAAUAVA0.JPG)
B. Types of solutions
1. Based on the nature of solute and solvent
Table 2. Types of solutions
TYPE SOLUTE SOLVENT EXAMPLE
Gas in gas O2 N2 air
Gas in liquid CO2 water soda water
Liquid in liquid ethanol water alcoholic bevarages
Solid in liquid NaCl water brine solution
Gas in solid H2 Pd metal hydrides
Liquid in solid Hg Au dental amalgam
solid in solid C Fe steel and alloys
2. Based on the amount of solute dissolved in a given amount of solvent
Saturated solution a solution that contains the maximum amount of solute that can be dissolved in a
given amount of solvent at a given temperature
Unsaturated solution a solution containing less dissolved solute than that needed to form a saturated
solution
Supersaturated solution a solution that contains a greater amount of dissolved solute than that needed
to form a saturated solution
3. Based on extent of ionization of solute in the solvent
A solution of a strong electrolyte contains substances that ionize or dissociate completely in the solvent to form
ions. Ionic compounds, strong acids and strong bases are strong electrolytes
A solution of a weak electrolyte contains substances that only partially dissociate or ionize in the solvent to
produce relatively few ions. Weak acids and bases are weak electrolytes
A solution of a non-electrolyte contains substances that do not form ions in solution. Polar covalent molecules
which are soluble in water as molecules instead of ions are non-electrolytes
SolubilityvsIonization
Compounds which are very soluble in water are not necessarily strong electrolytes. Hydrogen acetate, HC2H3O2 is very
soluble in water to form acetic acid but ionizes partially into ions. Barium hydroxide,Ba(OH)2, in the other hand, is not
very soluble, but the amount that does dissolve dissociates or ionizes completely
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VERGEL C. BUNGAY
(APPCHEN)
Table 3. Common strong acids and bases
STRONG ACIDS STRONG BASES
Group 1A metal
HCl HClO3
hydroxides such as
LiOH, NaOH, KOH,
HBr HClO4
RbOH and CsOH
Heavy group 2A metal
HI H2SO4*
hydroxides such as
*
only on the first Ca(OH)2, Sr(OH)2 and
HNO3 ionization Ba(OH)2
C. Concentration units
There are several ways of expressing concentration of a particular species in solution. The following are most
commonly used to express concentrations of solutions:
1. Weight percent usually used to express concentration of commercial aqueous reagents
wt weight of solute
% 100%

wt weight of solution
2. Volume percent commonly used to specify the concentration of a pure liquid compound diluted with
another liquid
vol volume of solute
% 100%
vol volume of solution
For alcoholic beverages, percentage of alcohol is usually expressed in terms of proof as follows:
vol
proof 2 %
vol
3. Weight/volume percent used to indicate the concentration of a solid reagent in a dilute aqueous solution
wt weight of solute (gram)
% 100%
vol volume of solution (mL)
4. Mole fraction (x) commonly used in unit operations to express concentrations of solute present in a stream
of gas or liquid
mole of solute
x
mole of solute mole of solvent
5. Molality (m) temperature-independent concentration term used conveniently in physicochemical
measurements of colligative properties of solutions
mole of solute (mol)
m
kilogram of solvent (kg)
6. Molarity (M) most commonly used in titration and denotes the amount of solute, in moles, dissolved in a
solvent and diluting to a final volume of 1L in a volumetric flask
mole of solute (mol)
M
volume of solution (L)
Formality (F) concentration term identical to molarity commonly used for solutions of ionic salts that do
not exist as molecule in solid or in solution
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VERGEL C. BUNGAY
(APPCHEN)
7. Normality (N) once popular unit of concentration still used by some chemists
equivalent of solute (eq)
N
volume of solution (L)
An equivalent represents the mass of material providing Avogadros number of reacting units. The number of
equivalents is given by the number of moles multiplied by the number of reacting units per molecule or atom.
m m
equivalent of solute
EW MW
f
where m = mass of solute [g], EW = equivalent weight [g-equiv1], MW = molar mass [g-mol1] and f =
molar equivalent [equiv-mol1]
Therefore, normality (N) is related to molarity (M) according to the following equation:
eq mol eq
Nf M
mol L L
Table 4. Molar equivalents of solutes

NATURE OF SOLUTE MOLAR EQUIVALENT
acid number of replaceable H+
base number of equivalent HO
salt net charge of an ion
oxidant gain of electron
reductant loss of electron
8. Solutes in trace concentrations

Table 5. Concentrations of solutes in trace concentrations
CONCENTRATION DEFINITION DIMENSIONS
wt gram solute mg solute g solute
parts per thousand pt 103 or
wt gram solution g solution kg solution
wt gram solute g solute mg solute
parts per million ppm 106 or

wt gram solute ng solute g solute
parts perbillion ppb 109 or
wt gram solute g solute mg solute
vol mL solution mL solution L solution
wt gram solute ng solute g solute
wt gram solute pg solute ng solute
parts pertrillion ppt 1012 or
vol volume solute nL solute L solute
vol volume solution mL solution L solution
vol volume solute pL solute nL solute
vol volume solution mL solution L solution
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VERGEL C. BUNGAY
(APPCHEN)
D. Factors affecting solubility
1. Solute-solvent interactions
Substances with similar intermolecular forces of attraction tend to be soluble in one another
Ionic and polar solutes dissolve readily in polar solvents.
Non-polar solutes are most likely to be soluble in non-polar solvents
2. Effect of pressure
The solubilities of solids and liquids are not appreciably affected by pressure while the solubility of
gases in any solvent increases as the pressure over the solvent increases
The solubility of a gas in a liquid is expressed by a simple equation known as Henrys Law
Figure3.Effect of pressure on the solubility of gases

3. Effect of temperature
In general, solubility of most solid solutes increases as the temperature of the solution of the solution
increases
For a dissolution process that is endothermic (heat is absorbed), an increase in temperature results to
increase in solubility of the solute (e.g. dissolution of KCl in water)
For a dissolution process that is exothermic (heat is released), an increase in temperature results to
decrease in solubility of the solute (e.g. dissolution of NH3 and HCl in water)
The solubility of gases decreases with increasing temperature
Figure 4. Solubility curve of

(a) gases and (b) polar
compounds in water
Source: (a) http://intranet.micds.org
and (b) http://files5.pdesas.org/
(a)(b)
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VERGEL C. BUNGAY
(APPCHEN)
4. Common ion
The presence of a common ion reduces the solubility of the salt as
predicted from the LChateliers principle
Consider the equilibrium between PbCrO4(s) and its ions in the solution
according to the reaction:
PbCrO4(s) Pb+2(aq) + CrO42(aq) (a) (b)
The addition of Na2Cr2O4 introduces the common ion, CrO42 in the Figure 5. (a) Saturated solution of
PbCrO4(s) and(b) formation of
solution and shifts the reaction to the right resulting to the formation of PbCrO4(s) upon adding Na2CrO4(s)
the precipitate, PbCrO4(s) Source: Brown et al 2004
E. Colligative Properties of Solutions

Physical properties of solutions which are dependent on the amount of the solute particles and not on the kind or
identity of the solute particles
1. Vapor pressure lowering
In the presence of a non-volatile solute in a solution, the vapor pressure of the resulting solution is less than
that of the pure solvent

P Psolvent Psolution Psolventxsolute
whereP = vapor pressure lowering, Psolvent = vapor pressure of pure solvent, Psolution = vapor pressure of the
resulting solution and xsolute = mole fraction of solute in the solution
2. Boiling point elevation
Similarly, the presence of a non-volatile solute, the boiling point the resulting solution is greater than that of
the pure solvent
TB TB,solution TB,solvent k Bm
whereTB = boiling elevation, TB,solution= boiling point of the resulting solution, TB,solvent= boiling point of the
pure solvent, kB = ebullioscopic constant (C kg solvent mol solute1) and m= molality (mol solutekg1
solvent). The ebullioscopic constant can be evaluated using the physical properties of the solvent as follows:
MWsolventRTB,2 solvent
kB
1000 H vap
whereMWsolvent = molar mass of the solvent (g mol1), R = 8.3145 103 kJ mol1 K1, TB, solvent= boiling
point of the pure solvent, Hvap = heat of vaporization of the solvent (kJ mol1)
3. Freezing point depression
When a solution freezes, crystals of pure solvent usually separate out since the solute is not soluble in the
solid phase of the solvent.As a result, the fraction of the solvent in the solution becomes lower and the
freezing point drops further.
TF TF,solvent TF,solution k Fm
whereTF = freezing point depression, TF,solvent= freezing point of the pure solvent, TF,solution= boiling point of
the resulting solution, kF = cryoscopic constant and m= molality (mol solute kg1 solvent). The cryoscopic
constant can be evaluated using the physical properties of the solvent as follows:
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VERGEL C. BUNGAY
(APPCHEN)
MWsolventRTF,2 solvent
kF
1000 H fus
whereMWsolvent = molar mass of the solvent (g mol1), R = 8.3145 103 kJ mol1 K1, TF, solvent= boiling
point of the pure solvent, Hfus = heat of vaporization of the solvent (kJ mol1)
4. Osmotic pressure
Osmosis is the spontaneous movement of solvent molecules through a semi-permeable membrane from a
less concentrated solution to a more concentrated solution
Osmotic pressure is the minimum pressure required to halt the net flow of solvent
MRT
where = osmotic pressure (atm), M = molarity (mol L1), R = 0.08205 LatmK1mol1 and T =
temperature (K)
Table 6.Cryoscopic and ebullioscopic constants of common solvents
SOLVENT FORMULA
MW TF Hfus kF TB Hvap kB
(g- mol1) (C) (kJmol1) (C/molal) (C) (kJmol1) (C/molal)
Acetic acid CH3COOH 60.05 16.6 12.09 3.07 118.2 24.39 3.90
Water H2O 18.02 0.0 6.0095 1.86 100.0 40.656 0.51
Benzene C6H6 78.11 5.53 9.837 5.12 80.1 30.765 2.53
Ethanol C2H5OH 46.07 114.6 5.021 1.99 78.5 38.58 1.22
Methanol CH3OH 32.04 97.9 3.167 2.58calc 64.7 35.27 0.86calc
Carbon tetrachloride CCl4 153.82 -22..9 2.51 29.8 76.7 30.0 5.02
Choloroform CHCl3 119.38 63.7 8.8 4.68 61.17 29.24b 3.63
Camphor C10H6O 152.23 178.35a 6.82a 37.8 207.4b 59.5b 4.91calc
Sources: Felder, R. M. and Rouseeau R.W., Elementary Principles of Chemical Processes, 3rd Edition, John Wiley & Sons Inc. (2005.
a
Frandsen, M., Cryoscopic constant, heat of fusion, and heat capacity of camphor. Bur. Stand. J. Res., 1931, 7, 477-483.
b
http://www.phs.d211.org//science/smithcw/AP%20Chemistry/Posted%20Tables/Enthalpy%20Vaporization%20and%20Fusion.pdf
5. Solutions of Electrolytes
For substances that produces ions in solution (strong and weak electrolytes), the vant Hoff factor, i is
included in the formula of the various colligative properties
Jacobus Henricus vant Hoff (1852-1911) proposed that for solutes that dissociates into n ions, the extent
of dissociation, is related as follows:
i 1

n 1
For most electrolytes, the value of i approaches the number of ions formed in solution. For non-
electrolytes, the value of i is equal to 1.
Therefore, the colligative properties of the electrolytes are expected to be greater than those of the non-
electrolytes.
For electrolytes, those that form more ions in solution have greater colligative properties
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VERGEL C. BUNGAY
(APPCHEN)
III. Stoichiometric Calculations in Reactions Involving Gas Mixtures
A. States and properties of matter
Table 7. Properties of the classical states of matter
States of Matter
Properties
Solid Liquid Gas
Density high high low
Compressibility incompressible slightly compressible very compressible
Volume and volume is definite but takes assumes the shape and
Shape shape and volume is definite
the shape of the container volume of the container
Molecular Motion vibrate on fixed positions slide past one another free motion
Other States of Matter

1. Plasma results from a mixture of neutral atoms, free electrons and charged ions, usually a fluid but due to
charged particles present, it responds to and generates electromagnetic forces
2. Bose-Einstein Condensate special state of matter in which atoms in a confined gas act together like a
single giant particle after being cooled cryogenically to a temperature near absolute zero
B. Pressure
defined as the force divided by the area to which the force is applied
Standard atmosphere refers to mean atmospheric pressure at mean sea level which is precisely equal to
101,325 Pa or 1 atm (Confrence Gnrale des Poids et Mesures, CGPM, 1954); however, replaced by
100,000 Pa or 1 bar (IUPAC, 1982)
Standard atmospheric pressure pressure exerted by a column of Hg at 0C given that the density of Hg at
this temperature is 13.59508 gcm3 and the acceleration due to gravity is 9.80665 ms2
Table 8. Pressure units and conversion
Units Symbol Value
Pascal1 Pa 1 Pa = 1 kg m-1 s-2
bar bar 1 bar = 1 105 Pa
atmosphere atm 1 atm = 101,325 Pa
torr2 Torr 760 Torr = 101,325 Pa
millimeters of mercury mm Hg 760 mm Hg = 101, 325 Pa
pound per square inch psi 14.6959494 psi = 101,325 Pa
1
named after Blaise Pascal (1623-1662); 2named after Evangelista Torricelli (1608-1647)
C. Temperature
Table 9. Temperature scales
Conversion of Temperature Scales
C 5
9
F 32 F 95 C 32 K C 273.15 R F 459.67 R 1.8 K
Celsius scale (C) - Anders Celsius and Carl Linnaues, Fahrenheit scale (F) - Daniel Gabriel Fahrenheit, Kelvin scale (K) -
William Thomson and Rankine scale (R) - William John Macquorn Rankine
D. Standard temperature and pressure (STP)
a condition in which the temperature is 273.15 K (491.67 R) and 1 atm and the molar volume of a gas is
22.414 Lmol-1 (359.0378 ft3lbmol-1)
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VERGEL C. BUNGAY
(APPCHEN)
E. Standard ambient temperature and pressure (SATP)

a condition in which the temperature is 298.15 K (536.67 R) and 1 bar and the molar volume of a gas is
24.789 L mol-1 (397.09 ft3 lbmol-1)
F. Kinetic molecular theory
1. Gases are considered to be composed of minute discrete particles called molecules
2. The molecules within a container are believed to be in ceaseless chaotic motion during which they collide
with each other and with the walls of the container
3. Inasmuch as the pressure of a gas within a container does not vary with time at any given pressure and
temperature, the molecular collisions must involve no energy loss due to friction. In other words, all
molecular collisions are perfectly elastic
4. The absolute temperature is a quantity proportional to the average kinetic energy of all molecules in a system
5. At relatively low pressures, the average distances between molecules are large compared with molecular
diameters, and hence the attractive forces between molecules may be considered negligible
6. Since the molecules are small compared with distances between them, their volume may be considered to be
negligible compared with the total volume of the gas
G. Ideal gas laws
PV Values of R
R 8.314
J
nT mol K
cal
n = 1 mol 1.987
mol K
n m/ M L atm
0.08206
mol K
MV RT PV ft 3 - psia
R 10.73
lbmol - R
m P T
m/V
PM
ISOBARIC ISOTHERMAL ISOCHORIC
RT
V R P R
k PV RT k k
T P T V
CHARLES LAW BOYLES LAW GAY-LUSSACS LAW
RT
V k
P
AVOGADROS PRINCIPLE
n n
Vi VT V RT
k
P RT
k Pi PT
i 1 i 1
n P n V
AMAGATS LAW OF DALTONS LAW OF
n n
ni nT PARTIAL VOLUME PARTIAL PRESSURE
ni nT
i 1 MIXTURE OF IDEAL GASES i 1
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VERGEL C. BUNGAY
(APPCHEN)
H. Ideal gas mixtures

1. Daltons Law of Partial Pressure
formulated by John Dalton (17661844)
The pressure of a mixture of gases is equal to the sum of the pressures each of its components (known as
the partial pressure) would exert if alone in the volume of the mixture at the same temperature [7]
2. Amagats Law of Partial Volumes or Amagats Law of Additive Volumes
formulated by Emile Hilaire Amagat (1841-1915)
The volume of a mixture of gases is the sum of the volumes of its components, each at the pressure
and temperature of the mixture
3. Grahams Law of Diffusion
formulated by Thomas Graham (18051869)
Diffusion is the gradual mixing of molecules of one gas with molecules of another
Effusion is proves in which a gas under pressure escapes through an extremely small opening
Statement of Grahams law
The rate of diffusion or effusion of a gaseous mixture under the same temperature and pressure is
inversely proportional to the square roots of their molar masses.
Mathematically,
From the equations of the various molecular speeds
2 R most probable speed
kT 8R
r where k mean speed
M 3R root - mean - square speed

At constant temperature,
k' r M1 1 t2
r and similarly for a mixture of ideal gases, 2
M r1 M2 2 t1 d k
I. Stoichiometry involving gases

1. Gases Collected or Measured Over Water
Gases that are commonly insoluble in water and lighter than air are usually collected in the laboratory by
a method known as water displacement
These gases are allowed to replace the water inside an inverted container which is initially filled and
submerged in water
Once trapped, the gases are considerably wet since they are saturated with water vapor
To calculate for the total pressure, the pressure exerted by water vapor must be considered and assuming
the gases are ideal, Daltons law of partial pressure applies:
PT Pdry gas PH 2O
where PT = total pressure of the gas mixture, Pdry gas = partial pressure of the dry gas and PH 2O =
vapor pressure of water at a given temperature
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VERGEL C. BUNGAY
(APPCHEN)
Figure 6. Gas collection and measurement. Source: [3] Section 10.6, p. 413
2. Reaction Involving Gases

Involves calculation of the volume of gases consumed or produced in chemical reactions
Coefficients in a balanced chemical reactions determines the relative amounts in moles of the reactants
and products in a reaction
The number of moles of a gas, in turn, is related to P, V and T
Molar Mass Molar Mass

mass A Coefficients of mass B
mole A mole B
Ideal Gas Equation BALANCED CHEMICAL EQUATION Ideal Gas Equation
P, V, T P, V, T
PV = nRT PV = nRT
Figure 7. Stoichiometric relationship of chemical reactions involving gases
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VERGEL C. BUNGAY
(APPCHEN)
J. Thermochemistry
A portion of thermodynamics that involves the relationship between chemical and physical changes and
energy changes involving heat and work
1. Important Terminologies
a. Thermodynamics - a physical science that deals with the study of the interrelation of the various forms
of energy and concerned with the transfer of heat and work in various physical and chemical processes
b. System portion of the universe under consideration
i. Open system (or control volume) type of system that allows transfer of both matter and energy;
ii. Closed system (or control mass) type of system that allows exchange of energy only; consists of a
fixed amount of mass while its volume does not have to be fixed
iii. Isolated system type of system that allows neither transfer of matter nor energy
matter matter matter

energy
energy energy
Figure 8. Types of systems

c. Surroundings portion of the universe other than the system
d. Boundary real/imaginary or fixed/moving surface that separates the system from its surroundings and
where exchange of matter or energy takes place
2. Nature of Energy
The energy of a system can be classified as follows:
a. Internal energy (U) refers to the total energy of the system in the molecular level which can be due to
the motion of molecules relative to the center of mass of the system, or to the rotational and vibrational
motion and the electromagnetic interactions of the molecules, or to the motion and interaction of the
atomic and subatomic components of the molecules
b. External energy refers to the energy of the system as a bulk which can be associated with the velocity
and location of its center of mass
c. Kinetic energy (KE) energy due to the translational motion of the system relative to some point of
reference or to the rotation of the system about an axis
d. Potential energy (PE) energy due to the position of the system in a potential field such as
electromagnetic field or gravitational field
3. Units of Energy
a. Joule (J) SI unit for energy named in honor of James Prescott Joule (1818-1889) who studied the
nature of heat and its relationship to work
b. calorie (cal) amount of energy required to raise the temperature of 1 gram of water by 1F
c. British thermal units (BTU or Btu) amount of energy required to raise the temperature of 1 pound of
water by 1F
d. Conversion Factors
1 J = 1 Nm = 1 kgm2s2 1 kgm2/s2 = 107 gcm2s2 (erg)
1 BTU = 1,055.06 J 1 BTU = 252.16 cal
1 cal = 4.1840 J 1 BTU = 778.17 ftlbf
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VERGEL C. BUNGAY
(APPCHEN)
4. Thermodynamic Functions
a. State or point functions functions that depend on the current state of the system and not on how the
system reaches that state
b. Path function functions that depend on the path followed during a process
5. Zeroth (0th) Law of Thermodynamics

Formulated by Ralph Howard Fowler (1889-1944)
Generalization principle of thermal equilibrium between thermodynamic systems in contact
Thermal equilibrium state that exists between two subsystems of equal temperature
If body A is in thermal equilibrium with body B, and the body B is in thermal equilibrium with body
C, then body A is in thermal equilibrium with body C.
6. First (1st) Law of Thermodynamics
First explicit statement was given by Rudolf Julius Emmanuel Clausius (1822-1888)
States that, The energy of the universe is constant.
Also a statement of the Law of Conservation of Energy: Energy can neither be created nor
destroyed but can only be changed from one form to another.
7. Concept of Heat and Work
a. Heat (Q or q) form of energy transferred from one body to another by virtue of a temperature
difference
Exothermic process process that results to the release of energy in the form of heat to the
surroundings
Examples:
Physical change: H2O (l) H2O (s) + heat
Chemical change: CH4 (g) + 2O2 (g) CO2(g) + 2H2O(l) + heat
Endothermic process process that results to the absorption of energy in the form of heat from the
surroundings
Examples:
Physical change: Hg (s) + heat Hg (l)
Chemical change: CaCO3 (s) + heat CaO (s) + CO2 (g)
b. Work (W) form of energy that results to motion of a body by virtue of an opposing force; energy
transfer associated with a force acting through a distance
8. Energy Balance for a Closed System
For a system that only involves only exchange of energy in the form of heat and work, the change in the
internal energy of the system is equal to the sum of the heat added to and removed from the system and the
work done on or done by the system:
U Q W
9. Sign Convention
Q
ou (+) + Q or q heat is absorbed by the system (endothermic)
t () Q in
SYSTEM
Q or q heat is released from the system (exothermic)
+ W work is done on the system (endergonic)
+)
Wou
t ()
Win (
W work is done by the system (exergonic)
Figure 9. Sign convention of heat and work

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VERGEL C. BUNGAY
(APPCHEN)
10. Evaluation of Heat (Q)
a. Heat capacity (C)
An extensive property that is equal to the ratio of the heat added to or removed from a substance to
the resulting temperature change (JK1)
For one mole of a substance,
Q H Q U
CP and similarly CV
T P k T P k T V k T P k
where CP = heat capacity at constant pressure and CV = heat capacity at constant volume
b. Specific heat (c)
An intensive property that is equal to the heat capacity per unit mass or mole of a substance
C dQ
c and therefore Q CT ncT or similarly Q CT mcT
n dT
11. Evaluation of Moving Boundary Work

Pext Pext
(a) Work done on the system - compression

W Pext V2 V1
Pext Pext Since V1 > V2, therefore W is positive
V1 V2 (b) Work done by the system expansion
W Pext V2 V1
V2 V1
Since V2 > V1, therefore W is positive
(a) (b)
Figure 10. Moving boundary work

12. Enthalpy (H)
Measure of the total energy of a thermodynamic system; includes energy required to create the
system (U) and the energy required to make room for the system by displacing its surroundings
thereby establishing its pressure (P) and volume (V)
Mathematical expression of enthalpy
H U PV
At constant pressure,
dH dU PdV VdP dU PdV
dH dU PdV
Standard enthalpy of formation
Heat involved in the formation of a compound from its elements in their most thermodynamically
stable state at 25C and 1 atm
C (graphite) + O2 (g) CO2 (g) fH= 393.50 kJmol1
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VERGEL C. BUNGAY
(APPCHEN)
Table 10. Standard Enthalpy of Formation (kJ mol-1) of Compounds at 25C
fH fH fH
COMPOUNDS COMPOUNDS COMPOUNDS
(kJmol-1) (kJmol-1) (kJmol-1)
HCl(g) 92.31 NH3(g) 46.19 CH4(g) 74.85
HBr(g) 36.23 SO2(g) 296.90 C2H6(g) 84.67
HI(g) 25.96 SO3(g) 395.18 C3H8(g) 103.8
HNO3(l) 173.23 NO2(g) 33.80 C4H10(g) 124.7
H2SO4(l) 811.32 NO(g) 90.37 C2H4(g) 52.28
NaCl(s) 411.00 H2O(g) 241.83 C2H2(g) 226.75
NaOH(s) 426.60 H2O(l) 285.84 C6H6(l) 48.66
Na2SO4(g) 1384.50 CO2(g) 393.50 CH3OH(l) 238.60
Na2CO3(s) 1130.90 CO(g) 110.52 C2H5OH(l) 277.63
Standard enthalpy of reaction (rxnH)
rxn H n f H products n f H reactants
Standard enthalpy of combustion (combH)

Heat released when one mole of a fuel was burned in the presence of oxygen gas to produce carbon
dioxide gas and liquid water at 25C and 1 atm
CH4 (g) + O2 (g) CO2 (g) + 2H2O (l) combH= 890.36 kJmol1
Hess Law
If a reaction proceeds via several steps, the heat of the overall reaction is the same as the algebraic
sum of the heats involved in various steps
Table 11. Standard Enthalpy of Combustion (kJ mol-1) of Compounds at 25C

combH combH combH
COMPOUNDS COMPOUNDS COMPOUNDS
(kJmol-1) (kJmol-1) (kJmol-1)
CH4(g) 890.36 C2H4(g) 1410.99 C2H5OH(l) 1366.91
C2H6(g) 1559.90 C3H6(g) 2058.40 C2H5OH(g) 1409.25
C3H8(g) 2220.00 C2H2(g) 1299.60 H2(g) 285.84
nC4H10(g) 2855.60 CH3OH(l) 726.60 C6H6(l) 3267.60
nC5H12(g) 3536.10 CH3OH(g) 764.00 C6H6(g) 3301.50
13. Calorimetry
involves measurement of heat involved in a
chemical reaction or physical change resistance thermometer
stirrer
Two types of calorimeter
(a) Open-type calorimeter oxygen inlet
operates at constant pressure igniter
heat measured is a direct measure of H sample
(b) Bomb-type calorimeter
operates at constant volume heater
heat measured is a direct measure of U water
Figure 11. Bomb calorimeter
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VERGEL C. BUNGAY
(APPCHEN)
Energy balance in a calorimeter
Qcal Qrxn 0 and Qcal Ccal T
where Ccal = heat capacity of the calorimeter (JK1), T = change in temperature in the calorimeter,
Qrxn = heat of reaction (J)
Note: Qrxn = rxnH (at P=k) and Qrxn = rxnU (at V=k)
Relationship between H and U
Definition of H H U PV
then H U PV
and PV PV solid PV liquid PV gas
If there is at least one gaseous product or reactant, then

PV PV gas ngas RT assuming gases are ideal
rxn H rxnU ngas RT where ngas ngas product ngas reactant
14. Thermodynamics of Phase Transition

Transition temperatures
Normal transition temperature - temperature at which two phases are in equilibrium at 1 atm
Standard transition temperature - temperature at which two phases are in equilibrium at 1 bar
Heat involved during phase transition
Sensible heat is the heat absorbed or released by a substance that results to change in
temperature but no phase change
Latent heat is the heat absorbed or released by a substance that results to change in phase but no
temperature change
Calculations in Phase Transition
T1 Tfus Tfus
1 2
5 4
T2 Tvap Tvap
Figure 12. Phase transition of any substance
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VERGEL C. BUNGAY
(APPCHEN)
Table 11. Enthalpy equations for phase transition of a pure substance
SENSIBLE LATENT
TRANSITION H HEAT HEAT
1 H1 mCP,solid Tfus T1
2 H 2 mH fus
3 H 3 mCP,liquidTvap Tfus
4 H 4 mH vap
5 H 3 mCP,vaporT2 Tvap
For constant pressure (1 atm) phase transitions involving water, the following constants are used:
Table 12. Constants for phase transitions involving water

TRANSITION Ttransition transitionH
Fusion 0C 6.008 kJmol1 (80 calg1)
Vaporization 100C 40.656 kJmol1 (540 calg1)
SPECIFIC HEAT (c) SOLID LIQUID VAPOR
1 1
(J mol K ) 37.15 75.48 33.58
(cal g1 K1) 0.50 1.00 0.45
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VERGEL C. BUNGAY
(APPCHEN)
K. Chemical or Reaction Kinetics
An area of chemistry that is concerned with the rate of reaction the changes in the concentration of reactants
and products in a chemical reaction
1. Factors affecting the rate of chemical reactions
a. Nature of reactants
Acid-base reactions, salt formation and ion-exchange reactions are generally fast reactions
Nature and strength of bonds in reacting molecules greatly affects the rate of its conversion to
products
b. Physical state of the reactants
When reactants are in the same phase (homogeneous), random thermal motion bring them into
contact
When reactants are in different phases, contact occurs only at the interface
c. Concentration of the reactants
The molecules present in the container, the more frequently they collide and the more often a
reaction occurs between them
The rate of reaction is then proportional to the frequency of collision between molecules
d. Reaction temperature
More collisions occur at higher temperatures at a given time
Temperature affects the kinetic energy of the molecules and thus the energy of the collisions
e. Presence of a catalyst
A catalyst is a substance that increases the rate of a reaction without being consumed in the reaction
Causes a lower activation energy which in turn makes the rate constant larger and the rate higher
Activation energy is the minimum amount of energy required for a reaction to occur
2. Reaction rate
defined as the change in the concentration of reactants and products per unit time
Consider the reaction, A B
With respect to reactant A,

change in concentration of A conc A at t2 conc A at t1
Rate of reaction
change in time t2 t1
At2 At1 A
Rate of reaction
t2 t1 t
With respect to product B,

change in concentration of B conc B at t2 conc B at t1
Rate of reaction
change in time t2 t1
Bt2 Bt1 B
Rate of reaction
t2 t1 t
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VERGEL C. BUNGAY
(APPCHEN)
Note:
By convention, the rate of reaction is a positive number
The concentration of reactants decreases over time; therefore the change in its concentration is
negative. On the other hand, the concentration of products increases over time; therefore the
change in its concentration is positive.
Square brackets, [ ] are used to express concentrations in moles per liter.
3. Average, instantaneous and initial reaction rates

Average reaction rate the change in the concentration over a period of time
Instantaneous reaction rate rate at a particular instant during the reaction and obtained by
determining the slope of the tangent line to the curve (plot of concentration versus time) at a particular
time
Initial reaction rate the instantaneous rate at the moment the reactants are mixed
Practice Problem 1. Consider the following concentrations of O3 as it reacts with C2H4 given the
reaction: C2H4(g) + O3(g) C2H4O(g) + O2(g)
Table A. Concentration of O3 at various times in its reaction with C2H4 at 303 K
[O3], molL1 3.20 105 2.42 105 1.95 105 1.63 105 1.40 105 1.23 105 1.10 105
t, s 0 10 20 30 40 50 60
Calculate the average reaction rate during the 60 s of the reaction
Practice Problem 2. If the plot of concentration can be estimated according to the cubic equation:
y = 1.0000 1010 t3 + 1.4869 108 t2 8.8179 107 t + 3.1895 105
Calculate the following:
a. Rate of reaction at 35 s
b. Initial reaction rate
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VERGEL C. BUNGAY
(APPCHEN)
4. Expressing rate in terms of reactants and product concentrations

Consider the reaction,
aA + bB cC + dD
where a, b, c and d are coefficients of the balanced equation. The rate is related to the reactant or product
concentrations as follows:
1 A 1 B 1 C 1 D
Rate
a t b t c t d t
Practice Problem 3. For the given reaction, the rate of consumption of O2 is 0.5 molL1:
2 H2 (g) + O2 (g) 2 H2O (g)
Calculate the following:
a. the rate of consumption of H2
b. the rate of formation of H2O
Practice Problem 4. Consider the following hypothetical reaction: 2 A (g) + 3 B (g) 4 C (g) + D(g)
Fill in the blanks.
a. The rate of consumption of A is __________ times the rate of consumption of B
b. The rate of consumption of A is __________ times the rate of formation of C
c. The rate of consumption of A is __________ times the rate of formation of D
d. The rate of consumption of B is __________ times the rate of formation of C
e. The rate of consumption of B is __________ times the rate of formation of D
f. The rate of formation of C is __________ times the rate of consumption of B
g. The rate of formation of C is __________ times the rate of formation of D
h. The rate of formation of D is __________ times the rate of consumption of A
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VERGEL C. BUNGAY
(APPCHEN)
5. Rate law
Rate of a chemical reaction is dependent only on the concentrations of the reactants and temperature
For a general reaction,
aA + bB cC + dD
the rate law expression is given by:
Rate k A B
m n
where k = reaction rate constant and the exponents, m and n = reaction orders
Note:
For a given reaction at a given temperature, the value of k does not change as the reaction
proceeds
However, k changes with temperature and therefore shows how temperature affects the rate
Coefficients a and b in the balanced chemical equation are not necessarily related in any way to
the reaction orders m and n
The components of the rate law rate, reaction orders and reaction constant are determined by
experiment and cannot be deduced from the reaction stoichiometry
6. Reaction orders
A reaction may have an individual order with respect to each reactant and an overall order which is
simply the sum of the individual orders.
First order unimolecular reaction
A reaction with a single reactant A is said to be first order in A if the rate is directly proportional to [A],
Rate = k [A]
Second order unimolecular reaction

A reaction with a single reactant A is said to be second order in A if the rate is directly proportional to
the square of [A], Rate = k [A]2
Zero order unimolecular reaction

A reaction with a single reactant A is said to be zero order in A if the rate is independent on [A], Rate =
k [A]0 = k
Practice Problem 5. Consider the gas-phase reaction: 2 NO (g) + 2 H2 (g) N2 (g) + 2 H2O (g). The rate law for
this reaction was determined to be Rate = k [NO]2 [H2]
Fill in the blanks.
a. The reaction is __________ order in NO
b. The reaction is __________ order with respect to H2
c. The reaction is __________ order overall
d. Doubling the concentration of H2 while keeping the concentration of NO constant increases the
reaction rate by __________ times
e. Doubling the concentration of NO while keeping the concentration of H2 constant increases the
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VERGEL C. BUNGAY
(APPCHEN)
Practice Problem 6. For the reaction: CHCl3 (g) + H2 (g) CH2Cl2 (g) + HCl (g). The rate law for this reaction
was determined to be Rate = k [CHCl3] [H2]
Fill in the blanks.
a. The reaction is __________ order in CHCl3
b. The reaction is __________ order with respect to H2
c. The reaction is __________ order overall
d. Quadrupling the concentration of H2 while keeping the concentration of CHCl3 constant increases the
e. Doubling the concentration of CHCl3 while keeping the concentration of H2 constant increases the
7. Determining the reaction orders and reaction rate constants experimentally

Method of initial rates
Series of experiments were performed using different set of reactant concentrations and obtaining
an initial rate in each case
The ratio of the rate laws were taken for experiments that change one reactant concentration while
keeping the other constant
The reaction rate constant and reaction order were evaluated from this ratio
Integrated rate laws
Suppose the rate law and the initial rate data are unknown, the concentration and time data can be
used directly to determine the reaction order
Initially, an order may be assumed and its corresponding linear form (Table 13) is plotted in the
x-y axis as shown in Fig. 13
If a straight line is obtained, then the order of the reaction is said to be of the assumed order
Figure 13. Linear plots of reactions at various reaction orders [3]
Half-life (t)
The time required for the concentration of the reactant to reach one-half its initial value:
A t
1
A0
1
2 2
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VERGEL C. BUNGAY
(APPCHEN)
Table 13. Summary of zero, first and second order reactions
ZERO ORDER FIRST ORDER SECOND ORDER
k A k A k A
0 1 2
Rate law expression
mol 1 L
Unit of k
L s s mol s
d A d A d A
k k A k A
2
Differential form
dt dt dt
At k t2 t1
At At
1 1
k t2 t1 ln k t 2 t1
At2 At1
2
At
Integral form 2 1
1
1 1
Linear form At kt A0 lnAt kt lnA0
At
kt
A0
Plot for straight line
x (abscissa) t t t
y (ordinate) [A] ln [A] 1/ [A]
Slope (m) k k k
y-intercept (b) [A]0 ln [A]0 1/ [A]0
A0 ln 2 1
k A0
Half-life, t
2k k
Practice Problems
7. Consider the gas-phase reaction between nitric oxide and bromine at 273C: 2 NO(g) + Br2(g)
NOBr (g). The following data for the initial rate of appearance of NOBr were obtained:
Experiment 1 2 3 4
[NO], molL1 0.10 0.25 0.10 0.35
[Br2], molL1 0.20 0.20 0.50 0.50
Initial rate, molL1s1 24 150 60 735
(a) Determine the rate law. (b) Calculate the average value of the rate constant for the appearance
of NOBr. (c) How is the rate of appearance of NOBr related to the rate of disappearance of Br 2?
(d) What is the rate of disappearance of Br2 when [NO] = 0.075 M and [Br2] = 0.25 M?
8. The following data were collected for the rate of disappearance of NO in the reaction: 2 NO(g) +
O2(g) NO2(g):
Experiment 1 2 3
[NO], molL1 0.0126 0.0252 0.0252
[O2], molL1 0.0125 0.0125 0.0250
Initial rate, molL1s1 1.41 102 5.64 102 1.13 101
(a) What is the rate law for the reaction? (b) What is the overall order of the reaction? (c) What is
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VERGEL C. BUNGAY
(APPCHEN)
the value of the rate constant of the reaction? (d) What is the rate of disappearance of O 2 when
[NO] = 0.0750 M and [O2] = 0.0100 M?
9. Sucrose (C12H22O11) which is commonly known as table sugar, reacts in dilute acid solutions to
from two simpler sugar, glucose and fructose. At 23C, the following data were obtained:
[C12H22O11], molL1 0.316 0.274 0.238 0.190 0.146
Time, min 0 39 80 140 210
Determine the order of the reaction with respect to sucrose and evaluate the reaction rate constant.
10. The gas-phase decomposition of NO2, 2 NO2(g) 2 NO(g) + O2(g), is studied at 383C, giving the
following data:
[NO2], molL1 0.100 0.017 0.0090 0.0062 0.0047
Time, s 0.0 5.0 10.0 15.0 20.0
Determine the order of the reaction with respect to NO2 and evaluate the reaction rate constant.
11. In a first-order decomposition reaction, 50.0% of a compound decomposes in 10.5 min. (a) What
is the rate constant of the reaction? (b) How long does it take for 75.0% of the compound to
decompose?
12. A decomposition reaction has a rate constant of 0.0012 yr1. (a) What is the half-life of the
reaction? (b) How long does it take for the reactant to reach 12.5% of its original value?
13. Biacetyl, the flavoring that makes margarine taste "just like butter," is extremely stable at room
temperature, but at 200C it undergoes a first-order breakdown with a half-life of 9.0 min. An
industrial flavor-enhancing process requires that a biacetyl flavored food be heated briefly at
200C. How long can the food be heated and retain 85% of its buttery flavor?
14. For the simple decomposition reaction, AB(g) A(g) + B(g), the rate = k[AB]2 and k = 0.2 L/mols.
How long will it take for [AB] to reach one-third of its initial concentration of 1.50 M? What is
[AB] after 10.0 s?
15. Liquid A decomposes by second order kinetics and in a batch reactor 50% of A is converted in a 5
minute run. How much longer would it take to reach 75% conversion?
8. Effect of temperature on reaction rate

In general, the rate of a reaction doubles with each rise in temperature of 10 K (or 10C)
The temperature-dependence of the reaction rate constant was proposed by Swedish chemist Svante
Arrhenius (1859-1927) according to the following equation:
Ea
k Ae RT
where A = frequency factor, Ea = activation energy (Jmol1), R = 8.314 Jmol1K1 and T = reaction
temperature (K). As T increases, the negative exponent becomes smaller, so the value of k becomes
larger, which means that the rate increases
To evaluate the activation energy Ea, the Arrhenius equation is linearized as follows:
Ea 1
ln k ln A
R T
A plot of ln k vs 1/T gives a straight line whose slope is Ea/R and whose y-intercept is ln A
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VERGEL C. BUNGAY
(APPCHEN)
If reaction constants at two temperatures are given, the Arrhenius equation can be rearranged to give
k2 E 1 1
ln a
k1 R T2 T1
The smaller the Ea (or the higher the temperature), the larger the value of k, and the faster the reaction.
Conversely, the larger the Ea (or the lower the temperature), the smaller the value of k, and the slower the
reaction.
Practice Problems
16. The rate constant of a reaction is 4.7 103 s1 at 25C, and the activation energy is 33.6 kJ/mol.
What is k at 75C?
17. The rate constant of a reaction is 4.50 105 L/mols at 195C and 3.20 103 L/mols at 258C.
What is the activation energy of the reaction?
18. The rate of the reaction CH3COOC2H5 (aq) + HO1(aq) CH3COO1(aq) + C2H5OH(aq) was measured
at several temperatures, and the following data were collected:
Temperature (C) 15 25 35 45
k (M1s1) 0.0521 0.101 0.184 0.332
Using these data, graph k versus 1/T and determine the value of Ea and A.
19. The temperature dependence of the rate constant for a reaction is tabulated as follows:
Temperature (K) 600 650 700 750 800
k (M1s1) 0.028 0.22 1.3 6.0 23
Calculate of Ea and A.
20. The activation energy of a certain reaction is 65.7 kJmol1. How many times faster will the
reaction occur at 50C than at 0C?
21. For the reaction:
NO (g) + O3 (g) NO2 (g) + O2 (g)
The frequency factor, A is 8.7 1012 s1 and the activation energy is 63 kJmol1. What is the rate
constant for the reaction at 75C?
22. Given the same reactant concentrations, the reaction:
CO (g) + Cl2 (g) COCl2 (g)
At 250C is 1.50 103 times as fast as the same reaction at 150C. Calculate the activation energy
for this reaction. Assume that the frequency factor is constant.
23. The rate constant of a first-order reaction is 4.60 104 s-1 at 350C. If the activation energy is 104
kJmol-1, calculate the temperature at which its rate constant is 8.80 104 s-1.
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VERGEL C. BUNGAY
(APPCHEN)
9. Reaction mechanisms
Process by which a reaction occurs
Describes in detail the order in which bonds are broken and formed and the changes in the structure in
the course of the reaction
a. Elementary reactions (Elementary processes)

reactions or processes that occur in a single event or step
reaction in which the rate law is based directly on its molecularity
Molecularity
The number of molecules that participates as reactants in an elementary reaction
Unimolecular reactions
Reactions that involve a single molecule in an elementary reaction
Bimolecular reactions
Reactions involving the collision of two reactant molecules
Termolecular reactions
These reactions involve simultaneous collision of three reactant molecules. Elementary reactions of
these types are far less probable than unimolecular or bimolecular processes and rarely encountered.
Table 14. Elementary reactions and their rate laws

MOLECULARITY ELEMENTARY REACTION RATE LAW
Unimolecular A products Rate = k [A]
Bimolecular A + A products Rate = k [A]2
A + B products Rate = k [A] [B]
Termolecular A + A + A products Rate = k [A]3
A + A + B products Rate = k [A]2 [B]
A + B + C products Rate = k [A] [B] [C]
b. Multistep mechanisms
Chemical equations for the elementary reactions in a multi-step mechanism always add to give the
chemical equation of the overall process
Step 1: NO2 (g) + NO2 (g) NO3 (g) + NO (g)
Step 2: NO3 (g) + CO (g) NO2 (g) + CO2 (g)
Overall: NO2 (g) + CO (g) NO2 (g) + CO2 (g)
In this reaction, note that NO3 is neither a reactant nor a product in the overall reaction it is
formed in one elementary reaction and consumed in the next reaction
NO3 in this reaction is called an intermediate
c. Rate-determining step (or rate-limiting step) for a multi-step mechanism

The overall rate of a reaction cannot exceed the rate of the slowest elementary step of its
mechanism
The slowest elementary step is the rate-determining step or rate-limiting step of the overall reaction
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VERGEL C. BUNGAY
(APPCHEN)
Mechanisms with a slow initial step

Consider the following two-step mechanism:
NO2 (g) + NO2 (g) (slow)

k
Step 1: 1
NO3 (g) + NO (g)
Step 2: NO3 (g) + CO (g) NO2 (g) + CO2 (g)
k2 (fast)
Overall: NO2 (g) + CO (g) NO2 (g) + CO2 (g)
Step 2 is much faster than Step 1; that is k2 >>> k1
The intermediate NO3 (g) is slowly produced in Step 1 and is immediately consumed in
Step 2
Since Step 1 is slow and hence the rate-limiting or rate-determining step, the rate law of
the overall reaction equals the rate law of Step 1
Step 1 being an elementary bimolecular reaction will have the rate law: Rate = k1 [NO2]2
Mechanisms with a fast initial step

Consider the reaction: 2 NO (g) + Br2 (g) 2 NOBr (g)
The experimental rate law for this reaction was found to be Rate = k [NO]2 [Br2]
With the given rate law, one possible mechanism is that the reaction occurs in a single termolecular
step as follows:
NO (g) + NO (g) + Br2 (g) 2 NOBr (g)
However, these reactions are so rare. As such, an alternative mechanism must be considered that
does not involve a termolecular step:

k1
Step 1: NO (g) + Br2 (g)
k_1
NOBr2 (g) (fast)
Step 2: NOBr2 (g) + NO (g)

k2
2 NOBr (slow)
Overall: 2 NO (g) + Br2 (g) 2 NOBr (g)
Note that in Step 1, two processes occur: a forward reaction with rate constant, k1 and
a reverse reaction with rate constant, k _ 1 . Step 1 therefore may be viewed as two
elementary reactions with the following rate law expressions:
Step 1: NO (g) + Br2 (g)
k1
NOBr2 (g) Rate = k1 [NO] [Br]
k_1
NOBr2 (g) NO (g) + Br2 (g) Rate = k_1 [NOBr2]
Since Step 2 the slower step is the rate-determining or rate-limiting step, the rate law for
this step governs the rate law of the overall reaction: Rate = k2 [NOBr2] [NO]
However, NOBr2 is an intermediate generated in Step 1 and therefore generally unstable
and occurs in low and unknown concentration.
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VERGEL C. BUNGAY
(APPCHEN)
An assumption can be made on the behavior of NOBr2 in the reaction. First, NOBr2 may
be assumed to be inherently unstable and it does not accumulate to a significant extent in
the reaction mixture.
NOBr2 can either dissociate to form NO and Br2 (reverse reaction of Step 1) or react
with NO to form NOBr (Step 2). With Step 1 occurring faster than Step 2, a dynamic
equilibrium may be assumed to occur on the forward and reverse reactions of Step 1,
that is, the rates of the forward and reverse reactions are equal. Thus, the rate law
expressions of the forward and reverse reactions can be equated as follows:
k1 [NO] [Br] = k_1 [NOBr2]
Rate of forward Rate of reverse
reaction reaction
Using this relationship between the rates of the forward and reverse reactions of Step 1
and the rate law of the slower step (Step 2)
Step 1 k1 [NO] [Br] = k_1 [NOBr2]
Step 2 Rate = k2 [NOBr2] [NO]
Thus, the resulting rate law expression will be
k kk
Rate k[ NOBr2 ][ NO] k2 1 [ NO][Br2 ] [ NO] 2 1 [ NO]2 [Br2 ]
k k _1
_1
kk
With 2 1 k , the rate law expression will then be Rate k [ NO]2 [Br2 ] which is
k _1
consistent with the experimental rate law
This further implies that the mechanism of the reaction involves only unimolecular and
bimolecular processes rather than a single termolecular step.
In general, whenever a fast step precedes a slow one, the concentration of an
intermediate is determined by assuming that equilibrium is established in the first step.
Practice Problems
24. What is the molecularity of each of the following elementary reactions? Write the rate law for
each?
a. 2 NO (g) N2O2 (g)
b. SO3 (g) SO2 (g) + O (g)
c. Cl2 (g) 2 Cl (g)
d. OCl1 (aq) + H2O (l) HOCl (aq) + HO1 (aq)
e. NO (g) + Cl2 (g) NOCl2 (g)
25. The decomposition of hydrogen peroxide is catalyzed by iodide ion. The catalyzed reaction is
thought to proceed by a two-step mechanism:
(1) H2O2 (aq) + I1 (aq) H2O (l) + IO1 (aq) (slow)
1 1
(2) IO (aq) + H2O2 (aq) H2O (l) + O2 (g) + I (aq) (fast)
a. Write the rate law for each elementary reaction of the mechanism
b. Write the chemical equation for the overall processes
c. Identify the intermediate, if any in the mechanism
d. Predict the rate law for the overall process
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VERGEL C. BUNGAY
(APPCHEN)
26. A proposed mechanism for the gas-phase reaction between chlorine and nitrogen dioxide is
(1) Cl2 (g) + NO2 (g) Cl (g) + NO2Cl (g) (slow)
(2) Cl (g) + NO2 (g) NO2Cl (g) (fast)
a. What is the overall reaction equation?
b. Identify the intermediate(s), if any.
c. What are the molecularity and the rate law for each step?
d. Is the mechanism consistent with the actual rate law: rate = k[Cl2] [NO2]?
27. The reaction: 2 NO (g) + Cl2 (g) 2 NOCl (g) obeys the rate law, rate = k [NO]2 [Cl2]. The
following mechanism has been proposed for this reaction:
(1) NO (g) + Cl2 (g) NOCl2 (g)
(2) NOCl2 (g) + NO (g) 2 NOCl (g)
a. What would be the rate law if the first step was rate-determining?
b. Based on the observed rate law, what can we conclude about the relative rates of the two
steps?
28. Consider the oxidation reaction of nitrogen monoxide:
2 NO (g) + O2 (g) 2 NO2 (g)
(1) NO (g) + O2 (g) NO3 (g) (fast)
(2) NO3 (g) + NO (g) 2 NO2 (g) (slow)
Assuming the first elementary step to be reversible, what would be the rate law of the reaction?
L. Chemical Equilibrium
1. Kinetics versus equilibrium
Kinetics applies to the speed of a reaction, the concentration of reactant consumed or the concentration
of product formed per unit time
Equilibrium applies to the extent of a reaction, the concentration of product that has appeared after an
unlimited time or once no further change occurs
2. Types of equilibrium systems
Homogeneous equilibria
Type of equilibria that involves similar phases: PCl5 (g) PCl3 (g) + Cl2 (g)
Heterogeneous equilibria
Type of equilibria that involves different phases: CaCO3 (s) CaO (s) + CO2 (g)
Physical equilibria
Type of equilibria that involves a physical change: H2O (l) H2O (g)
Chemical equilibria
Type of equilibria that involves a chemical change: AgCl (s) Ag+ (aq) + Cl1 (aq)
3. Concept of equilibrium
State of a system in which the net rate of all chemical reactions is zero
Occurs when the opposing reactions proceed at equal rates
The rate at which the products are formed from the reactants equals the rate at which the reactants are
formed from the products
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VERGEL C. BUNGAY
(APPCHEN)
Consider the equilibrium between NO2 and N2O4,
N2O4 (g) NO2 (g)
colorless brown
Starting with the colorless solid N2O4 gas, heating the N2O4 gas above its boiling point (21C) results
to the formation of the brown NO2 gas
Because the chemical reaction occurs in a closed system, the reaction will eventually reach an
equilibrium state where the rate at which N2O4 dissociates to form NO2 is the equal to the rate at which
two molecules of NO2 reacts to form N2O4 as shown in Fig. 14
Once equilibrium is achieved, the concentrations of NO2 and N2O4 no longer change with time which
results to an equilibrium mixture containing these gases
Figure 14. The NO2 N2O4 equilibrium

For the reversible reaction, N2O4 (g) NO2 (g), both the forward and the reverse reactions are
elementary reactions. Thus, the rate laws for these elementary reactions are:
Forward reaction: N2O4 (g)
k1
NO2 (g) Rate k1 [ N 2O4 ]
Reverse reaction: k_1
NO2 (g) N2O4 (g) Rate k _1 [ NO2 ]
where k1 and k_1 are the rate constants for the forward and reverse reactions, respectively.
At equilibrium, the rates of the forward reaction is equal to the rate of the reverse reaction:
k1 [ N 2O4 ] k _1 [ N 2O4 ]
Rearranging this equation yields
k1 [ NO2 ]
K eq
k _1 [ N 2O 4 ]
4. Equilibrium constant
a. Law of mass action
Postulated in 1864 by Cato Maximilian Guldberg (1836-1902) and Peter Waage (1833-1900)
States that at a given temperature, a chemical system reaches a state in which a particular ratio of
reactant and product concentrations is a constant
b. Writing equilibrium constant expression
Given the following general equilibrium equation:
fF + gG xX + yY
According to the law of mass action, the equilibrium condition is expressed by the expression:
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VERGEL C. BUNGAY
(APPCHEN)
K eq
aX x aY y
aF f aG g
where a is the activity of a substance which is evaluated as the ratio of the concentration or pressure
of the substance to a reference concentration (1 M) or a reference pressure (1 atm). Therefore, the
activity of a substance has no units and hence the equilibrium constant. For pure solids and liquids,
the activity is just equal to 1.
Note:
(1) The concentration of a pure liquid or pure solid has a constant value, that is, if its mass is
doubled, its volume also doubles. therefore its concentration in terms of the ratio of mass to
volume remains constant
(2) For a pure substance, the reference value is the concentration of the pure substance itself, as
such, the activity of any pure solid or liquid is always equal to 1
Equilibrium constant in terms of concentration

From the previous expression of Keq,
K eq
aX x aY y
aF f aG g
the activity (a) can be expressed in terms of concentration as the ratio of the molarity of a substance
(Mi) to a reference concentration, M = 1 M:
x y
[X] [Y]

KC
aX x aY y M M

[X] x [Y] y
aF f aG g f
[F] [G]
g
[F] f [G] g

M M
Equilibrium constant in terms of pressure
The activity (a) can also be expressed in terms of pressure as the ratio of the pressure of a substance
(Pi) to a reference pressure, P = 1 atm:
x y
PX PY

KP
aX x aY y P P P x PY y
f g X f
aF f aG g PF PG PF PG g

P P
Relationship of KC and KP
Consider the homogeneous gas-phase reaction,
f F (g) + g G (g) x X (g) + y Y (g)
Assuming the gases to be ideal, the concentration of a gaseous component in the reaction can be
expressed in terms of its pressure according to the following reaction:
M n P
V RT
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VERGEL C. BUNGAY
(APPCHEN)
Replacing the KC expression with pressure yields
x y
PX PY

RT PX PY RT f g x y K RT f g x y
x y
[X] x [Y] y RT
KC
[F] f [G] g PF
f
PG
g
PF f PG g P

RT RT
Rearranging gives the following relationship
KP KC RT KC RT
x y f g ngases
L atm
where ngases n gas,products ngas,reactants and R 0.08206
K mol
Practice Problems
28. Write the expressions for KC and KP for the following reactions. In each case, indicate whether
the reaction is homogeneous or heterogeneous.
a. 2 O3 (g) 3 O2 (g) d. 2 Ag (s) + Zn+2 (aq) 2 Ag+ (aq) + Zn (s)
b. Ti (s) + 2 Cl2 (g) TiCl4 (l) e. NO (g) + Cl2 (g) NOCl2 (g)
c. Ni(CO)4 (g) Ni (s) + 4 CO (g) f. HF (aq) + H2O (l) H3O+ (aq) + F1 (aq)
29. The equilibrium concentrations for the reaction between carbon monoxide and molecular
chlorine to form COCl2 (g) at 74C are [CO] = 0.012 M, [Cl2] = 0.054 M, and [COCl2] = 0.14 M.
Calculate the equilibrium constants Kc and Kp.
30. The equilibrium constant Kp for the reaction: 2NO2 (g) 2NO (g) + O2 (g) is 0.158 at 1000K. What
is the equilibrium pressure of O2 if the PNO2 = 0.400 atm and PNO = 0.270 atm? 0.347 atm What
is the KC for this reaction? 1.93 103 What is the total pressure at equilibrium? 1.017 atm What
is the mole fraction of O2 in the mixture? 0.341
5. Determining the equilibrium concentrations given initial concentrations and the equilibrium constant (KC or
KP)
a. Given concentrations in molarity (M)

31. For the synthesis of NH3, N2 (g) + 3 H2 (g) 2 NH3 (g), the equilibrium constant, KC at 375C is
1.2. Starting with [H2]0 = 0.76 M, [N2]0 = 0.60 M, calculate the concentration of each gas at
equilibrium
Tabulate the concentrations as follows:
N2 (g) + 3 H2 (g) 2 NH3 (g)
Initial (I): 0.60 M 0.76 M 0
Change (C): x 3x +2x
Equilibrium (E): 0.60x 0.763x 2x
From the tabulation, the change in the concentration (C) were expressed using a single variable x.
This implies that x moles of N2(g) reacts with 3x moles of H2(g) to form 2x moles of NH3(g) which
are all present in say one (1) liter of sealed reaction vessel to yield concentration in molarity (M).
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VERGEL C. BUNGAY
(APPCHEN)
The negative signs for reactants denote consumption while the positive sign for the product
denotes formation.
Substitute the equilibrium concentrations into the KC expression
KC
NH3 2 2 x2 1.2
N 2 H 2 3 0.60 x0.763 3x3
Simplifying this expression yields the following equation
32.4x4 + 44.064 x3 17.01248 x2 + 4.2696192 x 0.31606272 = 0
The roots for this equation are
x1 = 0.9383, x2 = 0.1092, x3 = 0.1563 + 0.2661i and x4 = 0.1563 0.2661i
since the first root of the equation is greater than the given concentrations, the second root (x2 =
0.1092) will be taken as the acceptable value for x.
Therefore, the equilibrium concentrations are
[N2] = 0.60 x = 0.4908 M, [H2] = 0.76 3x = 0.4324 M and [NH3] = 2x = 0.2184 M
b. Given amounts in moles

Practice Problem
32. The equilibrium constant, Kc for the reaction: H2 (g) + CO2 (g) H2O (g) + CO (g) is 4.2. Initially,
0.80 mol H2 and 0.80 mol CO2 are injected into a 5.0 L flask. Calculate the concentration of each
species at equilibrium.
The initial concentrations in molarity (M) are calculated from the initial amount given in terms of
moles and the total volume of the reaction vessel. The initial concentrations are then tabulated as
follows:
H2 (g) + CO2 (g) H2O (g) + CO (g)
Initial (I): (0.80/5) M (0.80/5) M 0 0
Change (C): x x x x
Equilibrium (E): 0.16x 0.16x x x
Substitute the equilibrium concentrations into the KC expression
KC
H 2 CO2 xx 4.2
H 2OCO 0.16 x0.16 x
x 0.1075M
Therefore, the equilibrium concentrations are
[H2O] = [CO] = x = 0.1075 M and [H2] = [CO2] = 0.16 x = 0.0525 M
c. Given KP
Practice Problem
33. Consider the heterogeneous equilibrium process: C (s) + CO2 (g) 2 CO (g). At 700C, the total
pressure is found to be 4.50 atm. If the equilibrium constant KP is 1.52, calculate the equilibrium
partial pressures of CO2 and CO.
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VERGEL C. BUNGAY
(APPCHEN)
2
PCO
For the given reaction, the KP expression is written as K P 1.52 .
PCO2
Given a total pressure of 4.50 atm at equilibrium, PT 4.50 PCO PCO2 , the equilibrium partial
pressure are calculated as follows:
2
PCO P2
PT PCO PCO2 PCO PCO CO 4.50
KP 1.52
PCO 1.96 atm and PCO2 2.54 atm
d. Equilibrium constants for reactions derived from a given reaction

Practice Problem
34. For the reaction: C (s) + CO2 (g) 2 CO (g), KP = 1.52. Evaluate KP for the following reactions:
a. 2 CO (g) C (s) + CO2 (g) KP,a = (KP)1
b. C (s) + CO2 (g) CO (g) KP,b = (KP)
6. Reaction quotient (Q)

Calculated by substituting the initial concentrations of the reactants and products into the equilibrium
constant expression, Keq
n
products
x
initial
Q k 1
n
reactants
y
initial
k 1
If Q > Keq system proceeds from right to left to reach equilibrium

Q < Keq system proceeds from left to right to reach equilibrium
Q = Keq system is at equilibrium
Practice Problem
35. For the synthesis of NH3, N2 (g) + 3 H2 (g) 2 NH3 (g), the equilibrium constant, KC at 375C is
1.2. Starting with [H2]0 = 0.76M, [N2]0 = 0.60M and [NH3]0 = 0.48M, evaluate the reaction
quotient, QC. Answer: QC = 0.875, since is QC less than KC, the system will proceed from left to
right to reach equilibrium
7. Le Chateliers principle
If an external stress is applied to a system at equilibrium, the system adjusts in such a way that the stress
is partially offset as the system reaches a new equilibrium position
Consider the equilibrium reaction: N2(g) + 3 H2(g) 2 NH3(g) H = 45 kJ/mol
Effects of changing the concentration
Increasing (or decreasing) the concentration of the reactants shifts the reaction forward
(backward). Increasing (or decreasing) the concentration of the products shifts the reaction
backward (forward). In the given reaction, removing NH3 in the reaction vessel shifts the reaction
forward while adding some NH3 shifts the reaction backward.
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VERGEL C. BUNGAY
(APPCHEN)
Effects of changing the pressure or volume

Increasing the pressure (or similarly decreasing the volume) of a system in equilibrium will shift the
reaction towards the formation of less number of gaseous molecules. On the other hand, decreasing
the pressure (or similarly increasing the volume) of a system in equilibrium will shift the reaction
towards the formation of greater number of gaseous molecules. In the reaction given, increasing the
pressure of the system will result in the formation of more ammonia.
Effects of changing the temperature
Increasing the temperature favors an endothermic reaction while decreasing the temperature favors
an exothermic reaction. For the reaction above, increasing the temperature will favor the backward
reaction being exothermic.
Effects of Adding the Catalyst
Adding a catalyst does not affect the equilibrium. The presence of a catalyst influences the rate of
the reaction. The catalyst increases the rate of reaction by lowering the activation energy of the
reaction.
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VERGEL C. BUNGAY
(APPCHEN)
M. Acid-Base Equilibria
1. Definitions and theories of acids and bases
Acids have a sour taste and cause certain dyes to change color. The word acid comes from the Latin
word acidus meaning sour.
The word base, in contrast, comes from an English word which means to bring low.
Table 15. Definitions of acids and bases

THEORIES ACID BASE
Arrhenius theory substances that dissociate in substances that dissociate in

Svante August Arrhenius (1859-1927) aqueous solution to form aH3O+ aqueous solution to form bHO
Brnsted-Lowry theory
Johannes Nicolaus Brnsted (1879-1947) proton donor proton acceptor
Thomas Martin Lowry (1874-1936)
Lewis theory species that accepts lone pair of species that donates lone pair
Gilbert Newton Lewis (1875-1946) electrons electrons
a
hydronium ion, protonated water or solvated proton; bhydroxide ion
2. Conjugate acid-base pairs

In any acid-base equilibrium, both the forward reaction and the reverse reaction involve proton transfer.
Consider the reaction of the acid HX with water:
HA (aq) + H2O (l) H3O+ (aq) + A1 (aq)
acid base conjugate acid conjugate base
In the forward reaction, HA donates a proton to H2O which makes HA a Bronsted-Lowry acid and H2O a
Bronsted-Lowry base
In the reverse reaction, H3O+ donates a proton to A1 which makes H3O+ a Bronsted-Lowry acid and A1
a Bronsted-Lowry base
An acid and a base such as HA and A1 that differs only in the presence or absence of proton are called a
conjugate acid-base pair.
3. Ionization reactions
Complete ionization
Partial ionization

4. Strengths of acids and bases
Strength of acids
A strong acid completely transfers its proton to a water molecule, leaving no undissociated
molecules in solution
HA (aq) + H2O (l) H3O+ (aq) + A1 (aq)
The two types of strong acids are:
1. Hydrohalic acids HCl, HBr and HI
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VERGEL C. BUNGAY
(APPCHEN)
2. Oxoacids in which the number of oxygen atoms exceeds the number of ionizable protons
by two or more such as HNO3, HClO3, HClO4 and H2SO4. For H2SO4, only the first
proton is ionized completely.
A weak acid
Table 8. Ionization constants of weak acids and bases

Weak acids Formula Ka1 K a2 K a3
Acetic CH3COOH 1.75 105
Benzoic C6H5COOH 6.30 105
Hydrocyanic HCN 7.20 1010
Hydrofluoric HF 6.70 104
Hydrogen sulfide H2S 9.10 108 1.20 1015
Oxalic HOOCCOOH 6.50 102 6.10 105
Phosphoric H3PO4 1.10 102 7.50 108 4.80 1013
Phosphorus H3PO3 5.00 102 2.60 107
Sulfuric H2SO4 1.20 102
2
Sulfurous H2SO3 1.30 10 5.00 106
Weak bases Formula Kb1 K b2
Ammonia NH3 1.75 105
Aniline C6H5NH2 4.00 1010
Diethyl amine (C2H5)2NH 8.50 104
Dimethyl amine (CH3)2NH 5.90 104
Ethyl amine C2H5NH2 4.30 104
Methyl amine CH3NH2 4.80 104
THAM (CH2OH)3CN 1.20 106
Triethyl amine (C2H5)3N 5.30 104
Trimethyl amine (CH3)3N 6.30 105
Ethylenediamine H2NC2H4NH2 8.50 105 7.10 108
Zinc hydroxide Zn(OH)2 4.40 105
Practice Problems
1. For the following reactions, identify the Bronsted-Lowry acid and Bronsted-Lowry base on the
left side of the reaction and also designate the conjugate acid and conjugate base on the right side
of the reaction:
a. HClO (aq) + H2O (l) H3O+ (aq) + ClO1 (aq)
b. HSO41 (aq) + H2O (l) SO42 (aq) + H3O+ (aq)
c. HCO31 (aq) + H2O (l) HO1 (aq) + H2CO3 (aq)
d. HPO42 (aq) + H2O (l) HO1 (aq) + H2PO41 (aq)
2. Write the ionization reaction(s) of the following acids and bases:
a. HBr d. HF g. NaOH j. NH3
b. HNO3 e. H2CO3 h. KOH k. CH3NH2
c. H2SO4 f. CH3COOH i. Ca(OH)2 l. NH2OH
5.
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VERGEL C. BUNGAY
(APPCHEN)
weak acid (WA)
pH logx
strong base (SB) acidic salt (AS)
KA WA
K
WB
x Mx K W 0 x Kx MK 0 K B
2 2
K W /K B AS
K W /K A BS
pH 14 logx weak base (WB)
strong acid (SA)
basic salt (BS)
Sources
1. Himmelblau, David M. (1996), Basic Principles and Calculations in Chemical Engineering, 6th Edition, Prentice-
Hall International
2. Bungay, V.C., Centeno, C.R., Medina, L.C. Salazar, C.M. and Olao, S.B. (2012) Reviewer for Chemical
Engineering Licensure Examination 3rd Edition, Manila Review Institute Inc.
3. Brown, T.L., Lemay, H.E. Jr., Bursten, B.E. and Burdge, J.R. (2009) Chemistry: The Central Science, 11th Edition,
Pearson Education South Asia Pte. Ltd.
4. http://www.profpaz.com/
5. http://intranet.micds.org
6. http://antoine.frostburg.edu/chem/senese/101/solutions/faq/why-salt-melts-ice.shtml
7. Woo, K. W. and Yeo, S. I. Daltons law vs. Amagats law for the mixture of real gases. The SNU Journal of
Education Research 127-134
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DE LA SALLE UNIVERSITY Page 1

Gokongwei College of Engineering

Figure 1.Activity Series of Metals(arranged in decreasing activity)

DISPLACE HYDROGEN FROM ACIDS

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B. Excess and Limiting Reagents

C. Fractional Yield and Purity

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2. Purity amount of substance sought present in a given amount of sample

II. Properties of Solutions

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Figure 2. Ionic and molecular compounds in water

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Table 4. Molar equivalents of solutes

8. Solutes in trace concentrations

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Figure3.Effect of pressure on the solubility of gases

Figure 4. Solubility curve of

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E. Colligative Properties of Solutions

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Other States of Matter

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E. Standard ambient temperature and pressure (SATP)

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H. Ideal gas mixtures

I. Stoichiometry involving gases

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2. Reaction Involving Gases

Molar Mass Molar Mass

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matter matter matter

Figure 8. Types of systems

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5. Zeroth (0th) Law of Thermodynamics

W work is done by the system (exergonic)

Figure 9. Sign convention of heat and work

11. Evaluation of Moving Boundary Work

(a) Work done on the system - compression

Figure 10. Moving boundary work

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Standard enthalpy of combustion (combH)

Table 11. Standard Enthalpy of Combustion (kJ mol-1) of Compounds at 25C

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If there is at least one gaseous product or reactant, then

14. Thermodynamics of Phase Transition

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Table 12. Constants for phase transitions involving water

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Consider the reaction, A B

With respect to reactant A,

With respect to product B,

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3. Average, instantaneous and initial reaction rates

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4. Expressing rate in terms of reactants and product concentrations

Last updated:2/23/2016 3:21:15 PM

Second order unimolecular reaction

Zero order unimolecular reaction

Last updated:2/23/2016 3:21:15 PM