Heat of Reaction

The amount of heat that must be added or removed during a chemical

reaction in order to keep all of the substances present at the same
temperature. If the pressure in the vessel containing the reacting system is
kept at a constant value, the measured heat of reaction also represents the
change in the thermodynamic quantity called enthalpy, or heat content,
accompanying the processi.e., the difference between the enthalpy of the
substances present at the end of the reaction and the enthalpy of the
substances present at the start of the reaction. Thus, the heat of reaction
determined at constant pressure is also designated the enthalpy of reaction,
represented by the symbol H. If the heat of reaction is positive, the reaction
is said to be endothermic; if negative, exothermic.

The prediction and measurement of the heat effects that accompany

chemical changes are important to the understanding and use of chemical
reactions. If the vessel containing the reacting system is so insulated that no
heat flows into or out of the system (adiabatic condition), the heat effect that
accompanies the transformation may be manifested by an increase or a
decrease in temperature, as the case may be, of the substances present.
Accurate values of heats of reactions are necessary for the proper design of
equipment for use in chemical processes.

Because it is not practical to make a heat measurement for every

reaction that occurs and because for certain reactions such a measurement
may not even be feasible, it is customary to estimate heats of reactions from
suitable combinations of compiled standard thermal data. These data usually
take the form of standard heats of formation and heats of combustion. The
standard heat of formation is defined as the amount of heat absorbed or
evolved at 25 C (77 F ) and at one atmosphere pressure when one mole of a
compound is formed from its constituent elements, each substance being in its
normal physical state (gas, liquid, or solid). The heat of formation of an
element is arbitrarily assigned a value of zero. The standard heat of
combustion is similarly defined as the amount of heat evolved at 25 C and at
one atmosphere pressure when one mole of a substance is burned in excess
oxygen. The method of calculating heats of reactions from measured values of
heats of formation and combustion is based on the principle known as Hesss
law of heat summation.

Germain Henri Hess

(August 7, 1802 November 30, 1850) was a Swiss-born
Russian chemist and doctor who formulated Hess's Law,
an early principle of thermochemistry.

Born in Geneva, Switzerland, his father was

an artist and in 1805 moved the family to Russia to find
work. Beginning in 1822, Hess studied medicine at
the University of Tartu. He qualified as a physician in
1825.

Hess turned to chemistry after a meeting with Jns Jakob Berzelius, the
famous Swedish chemist, and went to Stockholm University to study under
him. On his return to Russia, Hess joined an expedition to study the geology of
the Urals before setting up a medical practice in Irkutsk.

In 1830, Hess took up chemistry full time, researching and teaching, and
later became a professor at the Saint Petersburg Technological Institute. His
most famous paper, outlining his law on thermochemistry, was published there
in 1840. His principle, a progenitor for the first law of thermodynamics, came
to be called Hess's Law. It states that in a series of chemical reactions, the
total energy gained or lost depends only on the initial and final states,
regardless of the number or path of the steps. This is also known as the law of
constant heat summation.
Hess's other work concerned the investigation of minerals, including
analysis of silver telluride (Ag2Te), which was named Hessite in his honour.
He also discovered that the oxidation of sugars yielded saccharic acid. Hess
was the author of a textbook on chemistry that was the standard Russian
work for several decades. He died in St. Petersburg.

Exercises | Seatwork | Worksheet

Problems
1. Calculate H if a piece of metal with a specific heat of .98 kJkg1K1 and
a mass of 2 kg is heated from 22o C to 28o C.
2. If a calorimeter's H is +2001 Joules, how much heat did the substance
inside the cup lose?
3. Calculate the H of the following reaction: CO2 (g) + H2O (g) --> H2CO3 (g) if the
standard values of Hf are as follows: CO2 (g): -393.509 KJ /mol, H2O (g):
-241.83 KJ/mol, and H2CO3 (g) : -275.2 KJ/mol.
4. Calculate H if a piece of aluminum with a specific heat of .9 kJkg1K1
and a mass of 1.6 kg is heated from 286o K to 299o K.
5. If the calculated value of H is positive, does that correspond to an
endothermic reaction or an exothermic reaction?
Answers
1. H=q=cpsp x m x (T) = (.98) x (2) x (+6o ) = 11.76 kJ
2. Since the heat gained by the calorimeter is equal to the heat lost by
the system, then the substance inside must have lost the negative of
+2001 J, which is -2001 J.
3. H = vpHf(products) - vrHf(reactants) so this means that you
add up the sum of the H's of the products and subtract away the H of
the products: (-275.2kJ) - (-393.509kJ + -241.83kJ) = (-275.2) - (635.339) = +360.139 kJ.
4. H=q=cpsp x m x (T) = (.9) x (1.6) x (13) = 18.72 kJ
5. Endothermic, since a positive value indicates that the system
GAINED heat.

Energy of Activation
It is defined as the energy that
must be overcome in order for
a chemical reaction to occur. Activation
energy may also be defined as the
minimum energy required to start a
chemical reaction. The activation energy
of a reaction is usually denoted
by Ea and given in units of kilojoules per
mole.
Activation energy can be thought
of as the height of the potential barrier
(sometimes called the energy barrier)
separating two minima of potential
energy (of the reactants and products of
a reaction). For a chemical reaction to
proceed at a reasonable rate, there
should exist an appreciable number of
molecules with energy equal to or
greater than the activation energy.
At a more advanced level, the Arrhenius Activation energy term from the
Arrhenius equation is best regarded as an experimentally determined
parameter that indicates the sensitivity of the reaction rate to temperature.
There are two objections to associating this activation energy with the
threshold barrier for an elementary reaction. First, it is often unclear as to
whether or not reaction does proceed in one step; threshold barriers that are
averaged out over all elementary steps have little theoretical value. Second,
even if the reaction being studied is elementary, a spectrum of individual
collisions contributes to rate constants obtained from bulk ('bulb') experiments
involving billions of molecules, with many different reactant collision
geometries and angles, different translational and (possibly) vibrational
energies - all of which may lead to different microscopic reaction rates.
Negative activation energy: In some cases, rates of reaction
decrease with increasing temperature. When following an approximately
exponential relationship so the rate constant can still be fit to an Arrhenius
expression, this results in a negative value of Ea. Elementary reactions
exhibiting these negative activation energies are typically barrierless
reactions, in which the reaction proceeding relies on the capture of the
molecules in a potential well. Increasing the temperature leads to a reduced
probability of the colliding molecules capturing one another (with more

glancing collisions not leading to reaction as the higher momentum carries

the colliding particles out of the potential well), expressed as a reaction cross
section that decreases with increasing temperature. Such a situation no
longer leads itself to direct interpretations as the height of a potential spot.
Temperature independence and the relation to the Arrhenius
equation: The Arrhenius equation gives the quantitative basis of the
relationship between the activation energy and the rate at which a reaction
proceeds. From the Arrhenius equation, the activation energy can be
expressed as
where A is the frequency factor for the reaction, R is the universal gas
constant, T is the temperature (in kelvin), and k is the reaction rate coefficient.
While this equation suggests that the activation energy is dependent on
temperature, in regimes in which the Arrhenius equation is valid this is
cancelled by the temperature dependence of k. Thus, Ea can be evaluated
from the reaction rate coefficient at any temperature (within the validity of the
Arrhenius equation).
Catalysis
The relationship between activation
energy ( ) and enthalpy of formation (H)
with and without a catalyst, plotted against
the reaction coordinate. The highest energy
position (peak position) represents the
transition state. With the catalyst, the
energy required to enter transition state
decreases, thereby decreasing the energy
required to initiate the reaction.
A substance that modifies the transition
state to lower the activation energy is termed a catalyst; a biological catalyst
is termed an enzyme. It is important to note that a catalyst increases the rate
of reaction without being consumed by it. In addition, while the catalyst lowers
the activation energy, it does not change the energies of the original reactants
or products. Rather, the reactant energy and the product energy remain the
same and only the activation energy is altered (lowered).
Relationship with Gibbs free energy: In the Arrhenius equation,
the term activation energy (Ea) is used to describe the energy required to
reach the transition state. Likewise, the Eyring equation is a similar equation
which also describes the rate of a reaction. Instead of also using Ea, however,
the Eyring equation uses the concept of Gibbs free energy and the symbol
* to denote the energy of the transition state.

Svante August Arrhenius

(19 February 1859 2 October 1927) was
a Swedish scientist, originally a physicist, but
often referred to as a chemist, and one of the
founders of the science of physical chemistry.
He received the Nobel Prize for Chemistry in
1903. The Arrhenius
equation, lunar crater Arrhenius and the
Arrhenius Labs at Stockholm University are
named after him.
Arrhenius was born on February 19, 1859 at
Vik (also spelled Wik or Wijk), near Uppsala,
Sweden, the son of Svante Gustav and Carolina
Thunberg Arrhenius. His father had been a land
surveyor for Uppsala University, moving up to a supervisory position. At the
age of three, Arrhenius taught himself to read without the encouragement of
his parents, and by watching his father's addition of numbers in his account
books, became an arithmetical prodigy. In later life, Arrhenius enjoyed using
masses of data to discover mathematical relationships and laws. At age 8, he
entered the local cathedral school, starting in the fifth grade, distinguishing
himself in physics and mathematics, and graduating as the youngest and most
able student in 1876.
Arrhenius next received a travel grant from the Swedish Academy of
Sciences, which enabled him to study with Ostwald in Riga (now in Latvia),
with
Friedrich
Kohlrausch in Wrzburg,
Germany,
with Ludwig
Boltzmann in Graz, Austria, and with van 't Hoff in Amsterdam.
In 1889 Arrhenius explained the fact that most reactions require added
heat energy to proceed by formulating the concept of activation energy, an
energy barrier that must be overcome before two molecules will react.
The Arrhenius equation gives the quantitative basis of the relationship
between the activation energy and the rate at which a reaction proceeds.
In 1891 he became a lecturer at the Stockholm University College
(Stockholms Hgskola, now Stockholm University), being promoted to
professor of physics (with much opposition) in 1895, and rector in 1896.
He was married twice, first to his former pupil Sofia Rudbeck (1894 to
1896), with whom he had one son, and then to Maria Johansson (1905 to
1927), with whom he had two daughters and a son.

Greenhouse Effect: Arrhenius developed a theory to explain the ice

ages, and in 1896 he was the first scientist to attempt to calculate how

changes in the levels of carbon dioxide in the atmosphere could alter the
surface temperature through the greenhouse effect. He was influenced by
the work of others, including Joseph Fourier and John Tyndall. Arrhenius used
the infrared observations of the moon by Frank Washington Very and Samuel
Pierpont Langley at the Allegheny Observatory in Pittsburgh to calculate the
absorption of infrared radiation by atmospheric CO2 and water vapour. Using
'Stefan's law' (better known as the Stefan Boltzmann law), he formulated his
greenhouse law. In its original form, Arrhenius' greenhouse law reads as
follows:
if the quantity of carbonic acid [H2CO3] increases in geometric
progression, the augmentation of the temperature will increase nearly in
arithmetic progression.
The following equivalent formulation of Arrhenius' greenhouse law is still
used today: F = Ln( / )
Here
is carbon dioxide (CO2) concentration measured in parts
per million by volume (ppmv);
denotes a baseline or unperturbed
concentration of CO2, and F is the radiative forcing, measured in watts per
square meter. The constant alpha () has been assigned a value between five
and seven.

Josiah Willard Gibbs

Josiah Willard Gibbs (February 11, 1839
April 28, 1903) was an American scientist who
made important theoretical contributions to
physics, chemistry, and mathematics. His work
on the applications of thermodynamics was
instrumental
in
transforming physical
chemistry into a rigorous deductive science.
Together with James Clerk Maxwell and Ludwig
Boltzmann, he created statistical mechanics (a
term that he coined), explaining the laws of
thermodynamics as consequences of the
statistical properties of large ensembles of
particles. Gibbs also worked on the application
of Maxwell's equations to problems in physical
optics. As a mathematician, he invented
modern vector calculus (independently of the
British scientist Oliver Heaviside, who carried
out similar work during the same period).

In 1863, Yale awarded Gibbs the first American doctorate in engineering.

After a three-year sojourn in Europe, Gibbs spent the rest of his career at Yale,
where he was professor of mathematical physics from 1871 until his death.
Working in relative isolation, he became the earliest theoretical scientist in the
United States to earn an international reputation and was praised by Albert
Einstein as "the greatest mind in American history". In 1901 Gibbs received
what was then considered the highest honor awarded by the international
scientific community, the Copley Medal of the Royal Society of London, "for his
contributions to mathematical physics".
Commentators and biographers have remarked on the contrast between
Gibbs's quiet, solitary life in turn of the century New England and the great
international impact of his ideas. Though his work was almost entirely
theoretical, the practical value of Gibbs's contributions became evident with
the development of industrial chemistry during the first half of the 20th
century. According to Robert A. Millikan, in pure science Gibbs "did for
statistical mechanics and for thermodynamics what Laplace did for celestial
mechanics and Maxwell did for electrodynamics, namely, made his field a wellnigh finished theoretical structure."
Free Energy
Free Energy G :
obtained from a reaction.

The maximum amount of energy that can be

The total change in free energy is then

G = G products - G reactants
At constant pressure

G = H TS

The sign of G tells us a lot about the reaction

G > 0

Not spontaneous, requires energy to occur.

G < 0

Spontaneous, will occur on its own, releasing energy.

G = 0 (H = TS)
At equilibrium, no desire to go one way or the other (why reactions stop
at some point).

Gibbs energy (also referred to as G) is also the chemical potential that

is minimized when a system reaches equilibrium at constant pressure and
temperature. Its derivative with respect to the reaction coordinate of the
system vanishes at the equilibrium point. As such, it is a convenient criterion
of spontaneity for processes with constant pressure and temperature.

The Gibbs free energy, originally called available energy, was developed
in the 1870s by the American mathematician Josiah Willard Gibbs. In 1873,
Gibbs described this available energy as
the greatest amount of mechanical work which can be
obtained from a given quantity of a certain substance in a given
initial state, without increasing its total volume or allowing heat
to pass to or from external bodies, except such as at the close of
the processes are left in their initial condition.
The initial state of the body, according to Gibbs, is supposed to be such
that "the body can be made to pass from it to states of dissipated
energy by reversible processes." In his 1876 magnum opus On the Equilibrium
of Heterogeneous Substances, a graphical analysis of multi-phase chemical
systems, he engaged his thoughts on chemical free energy in full.

10

Exercises | Seatwork | Worksheet

Problem (1)
A second-order reaction was observed. The reaction rate constant at 3
C was found to be 8.9 x 10-3 L/mol and 7.1 x 10-2 L/mol at 35 C. What is the
activation energy of this reaction?
Solution:
Activation energy is the amount of energy required to initiate a
chemical reaction. The activation energy can be determined from reaction
rate constants at different temperatures by the equation
ln(k2/k1) = Ea/R x (1/T1 - 1/T2)
where, Ea is the activation energy of the reaction in J/mol R is the ideal
gas constant = 8.3145 J/Kmol T1 and T2 are absolute temperatures k1 and
k2 are the reaction rate constants at T1 and T2
Step 1 - Convert C to K for temperatures
T = C + 273.15
T1 = 3 + 273.15
T1 = 276.15 K
T2 = 35 + 273.15
T2 = 308.15 K
Step 2 - Find Ea
ln(k2/k1) = Ea/R x (1/T1 - 1/T2)
ln(7.1 x 10-2/8.9 x 10-3) = Ea/8.3145 J/Kmol x (1/276.15 K - 1/308.15 K)
ln(7.98) = Ea/8.3145 J/Kmol x 3.76 x 10-4 K-1
2.077 = Ea(4.52 x 10-5 mol/J)
Ea = 4.59 x 104 J/mol
or in kJ/mol, (divide by 1000)
Ea = 45.9 kJ/mol
Answer:
The activation energy for this reaction is 4.59 x 104 J/mol or 45.9
kJ/mol.
Problem (2)

11

A reaction that has a rate of 1.1e-10 1/sec at a temperature of 270 K and

a rate of 1.4e-10 1/sec at a temperature of 300 K.
Answer:
The resulting equation would be:
Activation Energy = 8.314e-3 x ((270 x 300) / (300 - 270)) * ln(1.4e-10 / 1.1e10)
The activation energy for the example reaction would be:
Activation Energy = 8.314e-3 x 2700 * ln(1.27) = 5.41 KJ / mole
Problem (3)
Using the following information:
A= 1x1014sec-1
Ea= 75x103 J/mol
R= 8.314 Jxmol/K
Calculate k at 27 C with proper units.
Answers:
k= 8.727 sec-1 (Remember to convert from Joules to Kelvin)
Problem (4)
Using information from problem 3, calculate k at 37 C with proper
units.
Answers:
k=23.02 sec-1

12

Problem (5)
Using the integrated equation solve for Ea using:
k1=7.78x10^-7
k2=3.46x10^-5
T1=273K
T2=298K
Answers:
Ea=1.026x10^5 J/mol

Exothermic and Endothermic Reaction

ENDOTHERMIC describes a process or reaction in which the system
absorbs energy from its surroundings in the form of heat. It is a modern
coinage from Greek roots. The prefix endo- derives from the Greek
word "endon" meaning "within," and the latter part of the word comes
from the Greek word root "therm" meaning "hot." The intended sense
is that of a reaction that depends on taking in heat if it is to proceed.
The opposite of an endothermic process is an exothermic process, one
that releases, "gives out" energy in the form of heat. Thus in each term
(endothermic & exothermic) the prefix refers to where heat goes as the
reaction occurs.
Examples

Photosynthesis

Melting ice

Thermal decomposition reactions

Forming a cation from an atom in the gas phase

Dissolving ammonium chloride in water

13

High-energy neutrons can also produce tritium from lithium-7 in an

endothermic reaction, consuming 2.466 MeV. This was discovered when
the 1954Castle Bravo nuclear test produced an unexpectedly high yield.

7
4
3
+
n

+
+
n
3Li
2He
1T
EXOTHERMIC ("outside heating") describes a process or reaction that
releases energy from the system, usually in the form of heat, but also
in the form of light (e.g. a spark, flame, or explosion), electricity (e.g. a
battery), or sound (e.g. burning hydrogen). Its etymology stems from
the prefix exo(derived from the Greek word ex, "outside") and the
Greek word thermasi (meaning "to heat"). The opposite of an
exothermic process is an endothermic process, one that absorbs
energy in the form of heat.
Examples

Condensation of rain from water vapor

Combustion of fuels such as wood, coal and oil petroleum

Mixing water and strong acids

Mixing alkalis and acids

The setting of cement and concrete

Some polymerisation reactions such as the setting of epoxy resin

Thermite reaction

14

Exothermic Processes
freezing water
solidifying solid salts
condensing water vapor
making a hydrate from an
anhydrous salt
forming an anion from an atom in
the gas phase
Annihilation of matter E=mc2
splitting of an atom

Exothermic Reactions
Combustion of hydrogen
dissolving lithium chloride in water
Burning of propane
dehydration of sugar with
sulfuring acid
decomposition of hydrogen
peroxide
decomposition of ammonium
dichromate
halogenation of acetylene

Endothermic Processes
melting ice cubes
melting solid salts
evaporating liquid water
making an anhydrous salt from a
hydrate
splitting a gas molecule
separating ion pairs
cooking an egg
baking bread

Endothermic Reactions
dissolving ammonium chloride in
water
reaction of thionyl chloride
(SOCl2) with cobalt(II) sulfate
heptahydrate
mixing water and ammonium
nitrate
mixing water with potassium
chloride
photosynthesis (chlorophyll is
used to react carbon dioxide plus
water plus energy to make
glucose and oxygen)

15

Marcellin Berthelot
Pierre
Eugne
Marcellin
Berthelot (25
October 1827 18 March 1907) was a French
Chemist and Politician noted for the ThomsenBerthelot Principle of thermochemistry. He
synthesized many organic compounds from
inorganic substances and disproved the theory of
vitalism. He is considered as one of the greatest
chemists of all time.
He was born in Paris, France, the son of a
doctor. After doing well at school in history and
philosophy, he became a scientist.
The fundamental conception that underlay all Berthelot's chemical work
was that all chemical phenomena depend on the action of physical forces
which can be determined and measured. When he began his active career it
was generally believed that, although some instances of the synthetic
production of organic substances had been observed, on the whole organic
chemistry remained an analytical science and could not become a constructive
one, because the formation of the substances with which it deals required the
intervention of vital activity in some shape. To this attitude he offered
uncompromising opposition, and by the synthetic production of
numerous hydrocarbons, natural fats, sugars and other bodies he proved that
organic compounds can be formed by ordinary methods of chemical
manipulation and obey the same principles as inorganic substances, thus
exhibiting the "creative character in virtue of which chemistry actually realizes
the abstract conceptions of its theories and classificationsa prerogative so
far possessed neither by the natural nor by the historical sciences."
In 1863 he became a member of the Acadmie Nationale de Mdecine;
he was also awarded the Grand Cross of the Legion of Honour.

16

Exercises | Seatwork | Worksheet

(1)What type of chemical reaction absorbs energy and requires energy for
the reaction to occur?
A: endothermic
C: synthesis
B: exothermic
D: both A and B
(2)What type of reaction releases energy and does not require initial energy
to occur?
A: endothermic
C: decomposition
B: exothermic
D: both A and B
(3)Which of the following are examples of an exothermic chemical reaction?
A: photosynthesis
C: freezing water into ice
B: burning a piece of wood
D: none of the above
(4)Which types of reactions are characteristic of negative heat flow?
A: endothermic
B: exothermic
C: neither
(5)Which type of reactions cannot occur spontaneously?
A: endothermic
B: exothermic
C: neither
(6)Which type of reaction is has a positive heat flow?
A: endothermic
B: exothermic
C: neither
(7)Any type of reaction that involves burning (combustion) can be classified
as which of the following types of reactions?
A: synthesis
C: exothermic
B: endothermic
D: all of the above
(8)Burning sugar is an exothermic process.
A: True
B: False
(9)Can a chemical reaction be both exothermic and endothermic?
A: Yes
B: No
(10)
What is enthalpy?
A: heat content
B: absolute amount of energy is a chemical system
C: the reactants of the chemical reaction
D: none of the above

Controlling Rates of Chemical Reactions

17

The study and control of chemical reaction rates are the subjects of
chemical kinetics. The rate of a chemical reaction depends on the nature of
the reaction and on variables of temperature and pressure, pH and reactant
concentrations. The presence of substances called catalysts also has major
effects on the rates of chemical reactions. Catalysts are often important, or
even crucial, because many reactions occur too slowly in their absence to be
of benefit or practical use.
RATES OF CHEMICAL REACTIONS
The rate of a chemical reaction is the change in concentration of a
reactant or of a product of the reaction, per unit change of time. Because
chemicals react, and products form, in molar ratios specific to a reaction, the
rate of a reaction must be specified in terms of individual reactants and
products. For example, in the reaction: C3H8 + 3H2O = 3CO + 7H2, H2
(hydrogen gas) is formed at seven times the rate at which C3H8 (propane) is
consumed.

CATALYSIS

A catalyst is a substance that increases the rate of a reaction but is not

itself consumed in the reaction so that the initial and final concentrations of
the catalyst are equal. The process of catalysis lowers the energy required for
chemical reactions to occur. Reactions then proceed much faster, in some
cases by many orders of magnitude. Catalysts do not change the equilibrium
position of a reaction. Catalysts are of two types: homogeneous and
heterogeneous.

HOMOGENEOUS CATALYSTS

A homogeneous catalyst is in the same phase as the reactants, usually

either the liquid or the gas phase. An example is the decomposition of
hydrogen peroxide, H2O2. The decomposition occurs in solution by a two-step
process, using an iodide ion (I-) as a catalyst: H2O2 + I- = IO- + H2O; H2O2 +
IO- = H2O + O2 + I-. The overall reaction is obtained by adding the two
reactions together, with the result: 2H2O2 = 2H2O + O2. Iodide is consumed
in the first reaction and regenerated in the second; therefore, it does not
appear in the overall reaction.

HETEROGENEOUS CATALYSTS

A heterogeneous catalyst is in a different phase than the reactants, the

catalyst frequently being a solid that provides a surface for arranging the
reactants in a way that favors reaction. For example, ethylene (C2H4) reacts
with hydrogen (H2), using solid platinum (Pt) as a catalyst, forming ethane, by
the reaction: C2H4 + H2 + Pt = C2H6. H2 molecules are adsorbed onto the Pt

18

surface, where they dissociate into hydrogen (H) atoms. The H atoms then
move over the Pt surface, where they encounter adsorbed C2H4 molecules.
The reaction is rapid because the energy required to break the H-H bond has
already been expended.

ENZYMES

Life would be impossible without organic catalysts called enzymes,

which are large protein molecules. More than 2,000 enzymes are known, and
every biochemical reaction is catalyzed by one specific enzyme. An example is
"peptidase," an enzyme that breaks peptide bonds in proteins. Peptidase does
not work with starch, which is broken down by "amylase" in the mouth.
Enzymes function by enfolding reactants into their complex structures,
bringing the reactants close together and into a geometry ideal for reaction.
Exercises | Seatwork | Worksheet
Give the right Term for each definition.
A short, easy way to show a chemical
reaction, using symbols
A chemical reaction in which two or more
simple substances combine to form a new,
more complex substance
A reaction in which one element replaces
another in a compound or when two
elements in different compounds trade
places
A system in which no matter is allowed to
enter or leave
a material that increases the rate of a
reaction y lowering the activation energy
A material used to decrease the rate of a
reaction
A system in which matter can enter from or
escape to the surroundings
A chemical reaction that breaks down
compounds into simpler products

Chemical Equation
Synthesis

Replacement
Closed System
Catalyst
Inhibitor
Open System
Decomposition

How Rates of Chemical Reaction affects our daily lives

It's useful to be able to predict whether an action will affect the rate at
which a chemical reaction proceeds. There are several factors that can

19

influence the rate of a chemical reaction. In general, a factor that increases

the number of collisions between particles will increase the reaction rate and
a factor that decreases the number of collisions between particles will
decrease the chemical reaction rate.
Concentration of Reactants
A higher concentration of reactants leads to more effective collisions per
unit time, which leads to an increasing reaction rate (except for zero order
reactions). Similarly, a higher concentration of products tends to be associated
with a lower reaction rate. Use the partial pressure of reactants in a gaseous
state as a measure of their concentration.

Temperature

Usually, an increase in temperature is accompanied by an increase in

the reaction rate. Temperature is a measure of the kinetic energy of a system,
so higher temperature implies higher average kinetic energy of molecules and
more collisions per unit time. A general rule of thumb for most (not all)
chemical reactions is that the rate at which the reaction proceeds will
approximately double for each 10C increase in temperature. Once the
temperature reaches a certain point, some of the chemical species may be
altered (e.g., denaturing of proteins) and the chemical reaction will slow or
stop.

Medium

The rate of a chemical reaction depends on the medium in which the

reaction occurs. It may make a difference whether a medium is aqueous or
organic; polar or non-polar; or liquid, solid, or gaseous.

Presence of Catalysts and Competitors

Catalysts (e.g., enzymes) lower the activation energy of a chemical

reaction and increase the rate of a chemical reaction without being consumed
in the process. Catalysts work by increasing the frequency of collisions
between reactants, altering the orientation of reactants so that more collisions
are effective, reducing intramolecular bonding within reactant molecules, or
donating electron density to the reactants. The presence of a catalyst helps a
reaction to proceed more quickly to equilibrium. Aside from catalysts, other
chemical species can affect a reaction. The quantity of hydrogen ions (the pH
of aqueous solutions) can alter a reaction rate. Other chemical species may
compete for a reactant or alter orientation, bonding, electron density, etc.,
thereby decreasing the rate of a reaction.

20

21

Chemical Equilibrium
In a chemical reaction, Chemical Equilibrium is the state in which both
reactants and products are present at concentrations which have no further
tendency to change with time. Usually, this state results when the forward
reaction proceeds at the same rate as the reverse reaction. The reaction
rates of the forward and reverse reactions are generally not zero but, being
9718equal; there are no net changes in the concentrations of the reactant and
product. This process is called dynamic equilibrium.
Chemical equilibrium applies to reactions that can occur in both
directions. In a reaction such as:
CH4(g) + H2O(g) <--> CO(g) + 3H2(g)
The reaction can happen both ways. So after some of the products are
created the products begin to react to form the reactants. At the beginning of
the reaction, the rate that the reactants are changing into the products is
higher than the rate that the products are changing into the reactants.
Therefore, the net change is a higher number of products.
Even though the reactants are constantly forming products and viceversa the amount of reactants and products does become steady. When the
net change of the products and reactants is zero the reaction has reached
equilibrium. The equilibrium is a dynamic equilibrium. The definition for a
dynamic equilibrium is when the amount of products and reactants are
constant. (They are not equal but constant. Also, both reactions are still
occurring.)
Equilibrium Constant
To determine the amount of each compound that will be present at
equilibrium you must know the equilibrium constant. To determine the
equilibrium constant you must consider the generic equation:
aA + bB <--> cC + dD
The upper case letters are the molar concentrations of the reactants
and products. The lower case letters are the coefficients that balance the
equation. Use the following equation to determine the equilibrium constant
(Kc).

22

Le Chatelier's Principle
Le Chatelier's principle states that when a system in chemical
equilibrium is disturbed by a change of temperature, pressure, or a
concentration, the system shifts in equilibrium composition in a way that tends
to counteract this change of variable. The three ways that Le Chatelier's
principle says you can affect the outcome of the equilibrium are as follows:

Changing concentrations by adding or removing products or reactants

to the reaction vessel.

Changing partial pressure of gaseous reactants and products.

Changing the temperature.

These actions change each equilibrium differently, therefore you must
determine what needs to happen for the reaction to get back in equilibrium.

Henri Louis Le Chtelier

Henri Louis Le Chtelier (8 October 1850 17
September 1936) was an influential French
chemist of the late 19th and early 20th
centuries. He is most famous for devising Le
Chtelier's principle, used by chemists to predict
the effect a changing condition has on a system
in chemical equilibrium.
In chemistry, Le Chtelier is best known for
his
work
on
his
principle
of
chemical
equilibrium, Le Chtelier's principle and on varying
solubility of salts in an ideal solution. He published no fewer than thirty papers
on these topics between 1884 and 1914. His results on chemical equilibrium
were presented in 1885 at the Acadmie des sciences in Paris.
Le Chtelier also carried out extensive research on metallurgy and was
one of the founders of the technical newspaper "La revue de mtallurgie."
Part of Le Chtelier's work was devoted to industry. For example, he was
a consulting engineer for a cement company, the Socit des chaux et
ciments Pavin de Lafarge, today known as Lafarge Cement. His 1887 doctoral
thesis was dedicated to the subject of mortars: Recherches exprimentales
sur la constitution des mortiers hydrauliques (Experimental Research on the
Composition of Hydraulic Mortars).

23

Le Chatelier in 1901 attempted the direct combination of the two gases

nitrogen and hydrogen at a pressure of 200 atm and 600C in presence of
metallic iron. The mixture of gases was forced by an air compressor into a
steel Berthelot bomb, where they and the reduced iron catalyst were heated
by a platinum spiral [from 4. "Henri Le Chatelier: His Publications," Ceram.
Abs., 16, (Oct., 1937)]. A terrific explosion occurred which nearly killed an
assistant. Sometime later Le Chatelier found that the explosion was due to the
presence of air in the apparatus used. And thus it was left for Haber to
succeed where a number of noted French chemists, including Thenard, Sainte
Claire Deville and even Berthelot had failed. In less than five years later, Haber
and Claude were successful in producing ammonia on a commercial scale,
acknowledging that the account of Le Chatelier's failed attempt had
accelerated their research. Near the end of his life, Le Chatelier wrote, "I let
the discovery of the ammonia synthesis slip through my hands. It was the
greatest blunder of my scientific career [from the last book by Henry Le
Chatelier De la Methode dans les Sciences Expkimentales," published in
1936, pp. 7376

Exercises | Seatwork | Worksheet

Problem (1)
A one-liter vessel contains 1.60 moles NH3, .800 moles N2, and 1.20
moles of H2. What is the equilibrium constant?

Answer:

1.85

Problem (2)
For the Haber process where the initial values are [N2(g)] = 1.23 M,
[H2(g)] = 5.00 M, and [NH3(g)] = 0 M.
Answer:
[N2(g)] = 1.23 M. [H2(g)] = 4.99 M, and [NH3(g)] = 0.00923 M

24

Problem (3)
For the Haber process where the initial values are [N2(g)] = 3.5 * 103 M,
[H2(g)] = 1.2 * 102M, and [NH3(g)] = 0 M.
Answer:
[N2(g)] = 3.5 * 103 M, [H2(g)] = 1.2 * 102 M, and [NH3(g)] = 1.8 * 1013 M

Problem (4)
For H2(g) + I2(g)

2HI(g) where the initial values are [H2(g)] = 2.5 M,

[I2(g)] = 10.0 M, and [2HI(g)] = 0 . Keq = 1.4 * 102. Note the quadratic
equation must be used to solve for x.
Answer:
[I2(g)] = 9.68 M. [H2(g)] = 2.18 M, and [HI(g)] = 0.632 M

25

Reversible and Irreversible Reaction

Irreversible Reactions
As children, we learned that chemical reactions occurred when reactants
reacted with each other to form products. These unidirectional reactions are
known as irreversible reactions. In other words, irreversible reactions are
reactions where the reactants convert to products and where the products
cannot convert back to the reactants. These reactions are essentially like
baking. The ingredients, acting as the reactants, are mixed and baked
together to form a cake, which acts as the product. This cake cannot be
converted back to the reactants (the eggs, flour, etc.), just as the products in
an irreversible reaction cannot change into the products.
As stated above, a cake cannot be "uncooked" and so the reaction is
irreversible.
A real-life example of an irreversible reaction is combustion. Combustion
usually involves the burning of an organic compound, like a hydrocarbon, and
oxygen to produce carbon dioxide and water. Since water is stable in its
polyatomic state, like below, it will not react with the other product, CO 2, to
form the reactants. Combustion can take the following form:
CxHy +
O2
CO2 + H2O
Reversible Reactions
In reversible reactions, the reactants and products are never used up. In
fact, they are both constantly reacting and being produced. A reversible
reaction can take the following summarized form:
A+BC+D
This reversible reaction can be broken into two reactions.
Reaction 1: A + B C + D
Reaction 2: C + D A + B
These two reactions are occurring simultaneously, which means that
the reactants are reacting to yield the products, as the products are reacting
to produce the reactants. Collisions of the reacting molecules cause chemical
reactions in a closed system. After products are formed, the bonds between
these products are broken because the molecules collide with each other,
producing sufficient energy needed to break the bonds of the product and
reactant molecules.
Below is an example of the summarized form of a reversible reaction
and a breakdown of the reversible reaction N2O4 2NO2

26

Reaction 1 and Reaction 2 happen at the same time because they are in
a closed system.
Blue: Nitrogen
Reaction 1

Red: Oxygen
Reaction 2

Imagine a ballroom. Let reactant A be 10 girls and reactant B be 10

boys. As each girl and boy goes to the dance floor, they pair up to become a
product. Once five girls and five boys are on the dance floor, one of the five
pairs breaks up and moves to the sidelines, becoming reactants again. As this
pair leaves the dance floor, another boy and girl on the sidelines pair up to
form a product once more. This process continues over and over again,
representing a reversible reaction.

27

Unlike irreversible reactions, reversible reactions lead to equilibrium

because reversible reactions have the reaction proceeding in both directions
while irreversible reactions only have the reaction proceeding in one direction.
If the reactants are being made at the same rate as the products are
being made, a dynamic equilibrium exists. For example, if a water tank is
being filled with water at the same rate as water is leaving the tank (through a
hypothetical hole), the amount of water remaining in the tank remains
consistent.
Connection to Biology
How Hemoglobin circulation is related to reversible reactions: There
are four binding sites on a hemoglobin molecule. Hemoglobin molecules
can either bind to carbon dioxide or oxygen. As your blood travels through
the alveoli of your lungs, hemoglobin molecules picks up oxygen-rich
molecules and binds to the oxygen. As the hemoglobin travels through the
rest of the body, it drops off oxygen at the capillaries for the organ system
to use oxygen. After expelling the oxygen, it picks up carbon dioxide. Since
this process is constantly carried out through the body, there are always
hemoglobin molecules that are picking or expelling oxygen and other
hemoglobin molecules that are picking up or expelling carbon dioxide.
Therefore, the hemoglobin molecules, oxygen, and carbon dioxide are
reactants while the hemoglobin molecules with oxygen or carbon dioxide
bound to them are the products. In this closed system, some reactants
convert into products as some products are changing into reactants,
making it like a reversible reaction.

28

Exercises | Seatwork | Worksheet

Problems
1.

What is the key difference between reversible and irreversible

reactions?

2.

Why is combustion an example of an irreversible reaction?

3.

How can a reversible reaction occur?

4.

Is the following hypothetical reaction reversible? A+ B C

5.

Why can't irreversible reactions lead to equilibrium?

Answers
1.

2.
3.

4.
5.

In a irreversible reaction, the reactants react to form the products,

which cannot revert back into reactants. In reversible reactions, as the
reactants react with other reactants to form products, the products are
reacting with other products to form reactants.
Combustion cannot be undone.
When the reactant molecules are placed in a closed environment, the
reactant molecules will collide with each other, producing energy that can
break the bonds between reactant and product molecules. Breaking such
bonds will allow the products to become reactants and the reactants to
become products.
No, it is not reversible, as indicated by the unidirectional arrow.
Irreversible reactions only proceed in one direction, so the reaction can
never be at equilibrium.

29

Equilibrium Constant
For a general chemical equilibrium
the thermodynamic equilibrium constant can be defined such that, at
equilibrium,

where curly brackets denote the activities of the chemical species. This
expression can be derived by considering the Gibbs free energy change for the
reaction. It is common practice to use concentrations, [A], rather than
activities, defining a concentration quotient, Kc.

Kc is equal to the thermodynamic equilibrium constant divided by a quotient of

activity coefficients, which, in certain circumstances, can have a value of 1; in
those cases Kc = K.
A knowledge of equilibrium constants is essential for the understanding
of many chemical systems, as well as biochemical processes such as oxygen
transport by hemoglobin in blood and acid-base homeostasis in the human
body.
Stability constants, formation constants, binding constants, association
constants and dissociation constants are all types of equilibrium constant.
See also Determination of equilibrium constants for experimental and
computational methods.
Types of equilibrium constants
(1)

Cumulative and stepwise formation constants

A cumulative or overall constant, given the symbol , is the constant for

the formation of a complex from reagents. For example, the cumulative
constant for the formation of ML2 is given by

30

The stepwise constant, K, for the formation of the same complex from
ML and L is given by

It follows that
A cumulative constant can always be expressed as the product of
stepwise constants. There is no agreed notation for stepwise constants,
though a symbol such as KL ML is sometimes found in the literature. It is best
always to define each stability constant by reference to an equilibrium
expression.
(1.1) Competition method
A particular use of a stepwise constant is in the determination of stability
constant values outside the normal range for a given method. For example,
EDTA complexes of many metals are outside the range for the potentiometric
method. The stability constants for those complexes were determined by
competition with a weaker ligand.

The formation constant of [Pd(CN)4]2- was determined by the competition

method.
(2)

Association and dissociation constants

In organic chemistry and biochemistry it is customary to use pKa values

for acid dissociation equilibria.

where Kdiss is a stepwise acid dissociation constant. For bases, the base
association constant, pKb is used. For any given acid or base the two constants
are related by pKa + pKb = pKw, so pKa can always be used in calculations.
On the other hand stability constants for metal complexes, and binding
constants for host-guest complexes are generally expressed as association
constants. When considering equilibria such as

31

it is customary to use association constants for both ML and HL. Also, in

generalized computer programs dealing with equilibrium constants it is
general practice to use cumulative constants rather than stepwise constants
and to omit ionic charges from equilibrium expressions. For example, if NTA,
nitrilotriacetic acid, N(CH2CO2H)3 is designated as H3L and forms complexes ML
and MHL with a metal ion M, the following expressions would apply for the
dissociation constants.

The cumulative association constants can be expressed as

Note how the subscripts define the stoichiometry of the equilibrium

product.
(3)

Micro-constants

When two or more sites in an asymmetrical molecule may be involved in

an equilibrium reaction there are more than one possible equilibrium
constants. For example, the molecule L-dopa has two non-equivalent hydroxyl
groups which may be deprotonated. Denoting L-Dopa as LH 2, the following
diagram shows all the species that may be formed (X=CH2CH(NH2)CO2H)

32

The first protonation constants are

[L1H] = k11[L][H], [L2H] = k12[L][H]
The concentration of LH- is the sum of the concentrations of the two
micro-species. Therefore, the equilibrium constant for the reaction,
the macro-constant, is the sum of the micro-constants.
K1 = k11 + k12
In the same way, K2 = k21 + k22
Lastly, the cumulative constant is

2 = K1K2 = k11k21 = k12k22

Thus, although there are six micro-and macro-constants, only three of

them are mutually independent. Moreover, the isomerization constant, Ki, is
equal to the ratio of the microconstants.
Ki = k11/k12
In L-Dopa the isomerization constant is 0.9, so the micro-species L 1H and
L H have almost equal concentrations at all pH values.
2

In general a macro-constant is equal to the sum of all the microconstants and the occupancy of each site is proportional to the microconstant. The site of protonation can be very important, for example, for
biological activity.
Micro-constants cannot be determined individually by the usual
methods, which give macro-constants. Methods which have been used to
determine micro-constants include:
blocking one of the sites, for example by methylation of a hydroxyl
group, to determine one of the micro-constants
using a spectroscopic technique, such as infrared spectroscopy, where
the different micro-species give different signals.

33

 applying mathematical procedures to

(4)

13

C NMR data.

pH considerations (Brnsted constants)

pH is defined in terms of the activity of the hydrogen ion

pH is measured by means of a glass electrode, a mixed equilibrium constant,

also known as a Brnsted constant, may result.

It all depends on whether the electrode is calibrated by reference to

solutions of known activity or known concentration. In the latter case the
equilibrium constant would be a concentration quotient. If the electrode is
calibrated in terms of known hydrogen ion concentrations it would be better to
write p[H] rather than pH, but this suggestion is not generally adopted.

(5)

Hydrolysis constants

In aqueous solution the concentration of the hydroxide ion is related to

the concentration of the hydrogen ion by

The first step in metal ion hydrolysis can be expressed in two different ways
1.
2.
It follows that * = KKW. Hydrolysis constants are usually reported in
the * form and this leads to them appearing to have strange values. For
example, iflg K = 4 and lg KW = 14, lg * = 4 + (14) = 10. In general when
the hydrolysis product contains n hydroxide groups lg * = lg K + n lg KW

34

(6)

Conditional constants

Conditional constants, also known as apparent constants, are

concentration quotients which are not true equilibrium constants but can be
derived from them. A very common instance is where pH is fixed at a particular
value. For example, in the case of iron(III) interacting with EDTA, a conditional
constant could be defined by

This conditional constant will vary with pH. It has a maximum at a

certain pH. That is the pH where the ligand sequesters the metal most
effectively.
In biochemistry equilibrium constants are often measured at a pH fixed by
means of a buffer solution. Such constants are, by definition, conditional and
different values may be obtained when using different buffers.
(7)

Gas phase equilibria

For equilibria in a gas phase, fugacity, f, is used in place of activity.

However, fugacity has the dimension of pressure, so it must be divided by a
standard pressure, usually 1 bar, in order to produce a dimensionless
quantity, f / p. An equilibrium constant is expressed in terms of the
dimensionless quantity. For example, for the equilibrium 2NO2
N2O4,

Fugacity is related to partial pressure, p, by a dimensionless fugacity

coefficient : f = p. Thus, for the example,

Usually the standard pressure is omitted from such expressions.

Expressions for equilibrium constants in the gas phase then resemble the
expression for solution equilibria with fugacity coefficient in place of activity
coefficient and partial pressure in place of concentration.

35

Cato Maximilian Guldberg

Cato Maximilian Guldberg (11 August 1836
14 January 1902) was a Norwegian mathematician
and chemist.
Gulberg worked at the Royal Frederick
University. Together with his brother-in-law, Peter
Waage, he proposed the law of mass action. This
law attracted little attention until, in 1877, Jacobus
Henricus van't Hoffarrived at a similar relationship
and experimentally demonstrated its validity.
In 1890, he published what is now known as the
Guldberg rule, which states that the normal boiling
point of a liquid is two-thirds of the critical
temperature when measured on the absolute scale.
From 1866 to 1868, 1869 to 1872 and 1874 to 1875 he was the
chairman of the Norwegian Polytechnic Society.

Peter Waage
Peter Waage (29 June 1833 13 January 1900), the son of a ship's captain,
was a significant Norwegianchemist and professor at the Royal Frederick
University. Along with his brother-in-law Cato Maximilian Guldberg, he codiscovered and developed the law of mass action between 1864 and 1879.
He grew up in Hidra. He was chairman of the Norwegian Polytechnic
Society from 1868 to 1869, and the first chairman of the Norwegian branch of
the YMCA when it was established in 1880.

36

Exercises | Seatwork | Worksheet

Problem (1)
Calculate the value of the equilibrium constant, Kc , for the system
shown, if 0.1908 moles of CO2, 0.0908 moles of H2, 0.0092 moles of CO, and
0.0092 moles of H2O vapor were present in a 2.00 L reaction vessel were
present at equilibrium.

Answer

Write the equlibrium expression for the reaction system.

Since Kc is being determined, checks to see if the given equilibrium

amounts are expressed in moles per liter (molarity). In this example they are
not; conversion of each is required.
[CO2] = 0.1908 mol CO2/2.00 L = 0.0954 M
[H2] = 0.0454 M
[CO] = 0.0046 M
[H2O] = 0.0046 M

Substitute each concentration into the equilibrium expression and

calculate the value of the equilibrium constant.

Problem (2)
A flask is charged with 3.00 atm of dinitrogen tetroxide gas and 2.00
atm of nitrogen dioxide gas at 25oC and allowed to reach equilibrium. It was
found that the pressure of the nitrogen dioxide decreased by 0.952 atm.
Estimate the value of Kp for this system:

Answer

37

Write the equilibrium expression to find Kp.

Create an ICE chart and calculate the changes in pressure and

equilibrium pressures for each species.
N2O4

NO2

3.00

2.00

Change in Pressure (atm)

+ 0.476

- 0.952

Equilibrium Pressure (atm)

3.476

1.048

Initial Pressure (atm)

Substitute the equilibrium pressures into the expression for Kp and

solve for Kp.

Problem (3)
Phosphorus pentachloride decomposes according to the reaction PCl5
PCl3 + Cl2 3 moles of PCl3 is placed in 1.0 liters closed vessel and allowed
to reach equilibrium at 523 K. Equilibrium constant Kc is 1.8. What is the
composition of the mixture of equilibrium?
Answer
Let us write the equilibrium constant expression
Kc = [PCl3] [Cl2]/ [PCl5]
The initial concentration of PCl5 is [PCl5] Initial = 3 mol. L-1
Let us construct the Equilibrium constant table
Compounds
PCl5

Initial Concentration
3.0 mol. L-1

Final Concentration
3.0 mol. -x L-1

38

PCl3

Cl2

X
X

Substituting the values from the table

Kc = [PCl3] [Cl2]/ [PCl5]
= x * x / (3.0 x) = 1.8
x calculated from this equation is 1.59.
So, equilibrium concentrations of all the compounds would be:
PCl5 = 3.0 1.59 = 1.41 mol/l
PCl3 = 1.59 mol/l
Cl2 = 1.59 mol /l
Problem (4)
A mixture of H2 and I2 is allowed to react at 448 degree Celsius.
When the equilibrium is established, the concentrations of participants are
[H2] = 0.46 mol/l, [I2] = 0.39 mol/l and [HI] = 3.0 mol/l. Calculate the Kc
value for the reaction.
Answer
Writing the equilibrium constant expression for the reaction:
Kc = [HI]2 / [H2][I2]
Lets substitute the values as:
Kc = [3.0]2 / [0.46] [0.39] = 50.
So, the equilibrium constant value for this reaction is 50. There are no
units, since concentration terms on the top and the bottom cancel out each
other.
Problem (5)
At 700K, the equilibrium constant Kc is 3.1 x 10-7 mol/l. Calculate the
Kp for the reaction. 2SO3 (g) --> 2SO2 (g) + O2 (g)
Answer
For the reaction: n = (2+1) = 3.
Kp = Kc (RT) n

39

R = gas constant = 0.082 L. atm/K. mol

T = 700 Kelvin.
Substituting the values for delta n, R and temperature, the value of Kp
would be equal to:
Kp = 1.78 x 10-5 atm.

Factors affecting rates of Equilibrium

Concentration, temperature and pressure effect chemical equilibrium.
We explain them in detail one by one. However, we first give you Le
Chatelier's principle of equilibrium;
Concentration. If the concentration of one ingredient is changed, the
equilibrium is lost.
Temperature. Change in temperature shifts the equilibrium to the
favourable side.
Catalyst involved in the reaction. Presence of a catalyst may affect
either side of the reaction, thereby destroying the equilibrium.
"If one of the factors like temperature, pressure or concentration of
system is changed then system react this change to conserve equilibrium."
1. Affect of Concentration on Equilibrium:
Adding or removing matters into reaction effect equilibrium. For
example, adding reactants or removing products increase the yield of
product. On the contrary, adding products or removing reactants increase
yield of reactants. I other words, in first situation equilibrium shifts to the
right and in second situation equilibrium shifts to the left. For instance; H2(g)
+ I2(g) 2HI(g)
If we add H2 gas to the container, equilibrium shifts to the right and
system decrease the concentration of H2. (Le Chatelier's principle)
2. Affect of Temperature on Equilibrium:

40

Heat must be given to system at equilibrium to increase temperature

of it. This process gives different results in endothermic and exothermic
reactions. For example;
H2(g) + I2(g) 2HI(g) + Heat
Reaction given above is exothermic. To keep equilibrium temperature
must be constant. If heat is given to system, according to Le Chatelier's
principle system wants to decrease this temperature and equilibrium shift to
the left or right. Equilibrium constant of this reaction;
Kc = [HI]2/([I2].
[H2])

In an endothermic reaction; increasing temperature shift equilibrium to

the right and equilibrium constant increases.

In an endothermic reaction; increasing temperature shift equilibrium to

the left and equilibrium constant decreases.
3. Affect of Pressure on Equilibrium:
To talk about affect of pressure on equilibrium, at least one of the
matters must be in gas phase. In other words, in a reaction consisting of
liquid, aqueous, or solid there is no affect of pressure on equilibrium of this
system.

If one of the matters in container under constant temperature and

pressure is removed or added, pressure of the system changes. However,
change in the concentration is taken into consideration not pressure.

Temperature can be changed under constant volume. In this situation

even if pressure changes, we consider changes in the temperature while
finding equilibrium constant.

In gas reactions, if there is no change in number of moles, then

pressure do not effect equilibrium.
Exercises | Seatwork | Worksheet
Three container given below are in equilibrium with given reactions.

41

If volumes of them decreased from point I to II, find in which container

equilibrium shifts to the right.
Solution:
I. In first container, there is no change in the number of moles. Thus,
pressure does not effect this reaction.
II. In second container, there is no change in the total number of moles. But,
in this reaction moles of gas in this reaction decreases. So, equilibrium
shifts to the right.
III. As you can see from the reaction, number of moles of decreases. Thus
equilibrium shifts to the right.

42

~ Table of Contents ~

p 01
p 04

Heat Of Reaction
Energy Of Activation
p 12
Exothermic And Endothermic Reaction
Controlling Rates Of Chemical Reaction
p 16
How Rates Of Chemical Reaction Affects Our
p 18
Daily Lives
Chemical Equilibrium
p 20
Reversible And Irreversible Reaction
Equilibrium Constant
p 24
Factors Affecting Rates Of Equilibrium
p 28
p 37

43