Pharm Chem 11

THERMOCHEMISTRY
& THERMODYNAMICS

Prepared by: N.M. Hinaut, RPh

 Pharm Chem 11

At the end of this lecture,

students are expected to:

 demonstrate understanding of the concepts of

thermochemistry and thermodynamics

 demonstrate understanding of the appplication of

thermochemistry & thermodynamics to pharmaceu
tical and medicinal chemistry
 Pharm Chem 11

THERMOCHEMISTRY
DEFINITION
 study of heat changes that accompany
chemical reactions and phase changes
 study of ENERGY ( in the form of HEAT)
released or absorbed as a result of che
mical reactions
 or the study of energy and heat associa
ted with chemical changes and physical
transformation
 Pharm Chem 11

Thermochemistry
IMPORTANCE
 Helps us determine if a reaction will occur
and if it will release or absorb energy.

 Helps us determine how much an energy a rea

ction will release or absorb to help us de
termine if it economically viable to use a
particular chemical process or not
 Pharm Chem 11
c
T h FIELDS
h e
e m
r i HEAT ENERGY WORK
m s
o t
r
y
HEAT
 Pharm Chem 11

Thermochemistry
HEAT

 an energy that transfers from one object to

another because of a temperature differenc
e between them

 Heat flows or transfer takes place from war

m (higher temp) to cool (lower temp) until
the two objects are at the same Temp.
 represented by “q” symbol
 Pharm Chem 11
c
T h Types of energy chemical reaction
h e
e m
r i
m s
o In exothermic processes,
t  the system loses or releases heat as its surroundings warm up.
r  q has a negative value (-) b/c the system is losing heat

y In endothermic processes,
 the system gains or absorbs heat as its surroundings cool down.
 q has a positive(+) value b/c the system is gaining heat.
 Pharm Chem 11

Thermochemistry
Example:
You are holding a hot water
bottle;

 What will happen?

 Will heat be transferred?
 Pharm Chem 11
c
T h HEAT TRANSFER
h e
Example :You are holding a hot water bottle,
e m What will happen? Will heat be transferred?
r i ▪ The warmer object (hot water
m s bottle) will transfer energy
to the cooler object (your hand.
o t ▪ When energy is transferred as heat,
the temperature of the water falls
r while the temperature of your skin rises.
▪ The great the difference in temperature of the two
y object, the more energy that will be transferred.
▪ This explains why hot things always cool down.
 Pharm Chem 11

Thermochemistry
Measuring Heat Flow
SI Unit of heat flow: Joule (J)

• Common unit used in chemistry: calorie (cal) –

Amt. of heat needed to raise 1 gram of water
by 1ºC.
1 cal = 4.184 J

• Food Calorie (capital “C”) = 1000 cal, or

1 kilocalorie = 4184 J
 Pharm Chem 11

Thermochemistry
HEAT CAPACITY
 Amount of heat needed to raise an object’s
temperature by 1°C.

 Depends on the chemical composition and the

mass of the object.
 more heat is required to raise the temp.
of a large sample of a substance by 1oC
than is needed for a smaller sample
 Pharm Chem 11

Thermochemistry
SPECIFIC HEAT CAPACITY
 Amount of heat needed to raise 1 gram of a substance
’s temperature by 1ºC.
– expressed in J/g ºC, or cal/g ºC

• The higher a substance’s specific heat, the more

energy it takes to heat it.

• Substances with low specific heat capacity,heats up

and cool down quickly (most metals, e.g.)
 Pharm Chem 11
c
T h Heat Capacity
h e EXAMPLE
e m
 1 gram of water requ
r i ires 1cal to raise
its temperature by
m s 1°C
o t  10 grams of water
r require 10 cal to
raise the temperatur
y by 1°C
 Pharm Chem 11
c
T h Specific Heat Capacity
h e also a physical property of matter that descri
e m bes matter’s resistance to a change in temper
r i ature.
m s the symbol for specific heat is Cp.
o t
r Not all substances heat up at the same rate ...
some get hot quickly and some more slowly...
y
 Pharm Chem 11

Thermochemistry
Specific Heat Capacity
EQUATION
 Pharm Chem 11
c
T h Specific Heat Capacity
h e
e m
r i
m s
o t
r
y
 Pharm Chem 11

Thermochemistry
Specific Heat Capacity
 Water has a very high specific heat compared to other
matter; therefore ocean water stays about the same tem
perature throughout day and night despite the differen
ces in temperature between night and day.

 That also explains why water is used in car radiators

to cool the engine.
 Pharm Chem 11
c
T h Specific Heat Capacity
h e
 Low specific heat
e m  less energy required to change the temperature
r i
 High specific heat
m s  more energy required to change the temperature
o t Which would get hotter if left under the sun?
r  Penny vs. Water
 Keys vs. soccer ball
y  Plastic recycling bin vs. metal trash can
 Pharm Chem 11

Thermochemistry
Specific Heat Capacity
EXAMPLE PROBLEMS
 Pharm Chem 11
c
T h Caloric Theory
h e  In the mid-19th century, the most accepted notion o
f heat was one that associated it with a fluid known
e m as caloric.
 heat was material in nature. It was a physical s
r i ubstance. It was stuff.
 Like all stuff in Lavoisier's world, calorie was a con
m s served substance.
o t  Similar to our modern view of heat, the calorist vie
w was that if caloric was released by one object, the
r n it was gained by another object.
 The total amount of caloric never changed; it was si
y mply transferred from one object to another and tra
nsformed from one type to another type
 Pharm Chem 11
c
T h Caloric Theory
h e  two forms of caloric :
 LATENT – a caloric that was stored in combustible
e m materials
r i  SENSIBLE – a caloric observed through a temperat
ure change
m s
 This theory had its fall – challenged by Benjamin Tho
o t mpson
 Through a boring process, he immersed the cannon
r in a tank of water during the boring process and o
y bserved that the heat generated by the boring proc
ess was capable of boiling the surrounding water
within a few hours.
 Pharm Chem 11
c
T h Caloric Theory
h e  English physicist James Prescott Joule took up where Thomp
e m son left off, delivering several fateful blows to the Caloric th
eory through a collection of experiments.
r i  Joule, for whom the standard metric unit of energy is now na
m s med, performed experiments in which he experimentally rel
ated the amount of mechanical work to the amount of heat
o t transferred from the mechanical system.
 Joule proved that in chemical reactions, a portion of this
r energy can be released to the surroundings in the form o
f heat. However, this internal energy is not a material su
y bstance or a fluid contained by the object. It is simply th
e potential energy stored in the bonds that hold particles
within the object together.
 Pharm Chem 11
c
T h Calories in Food
h e
 For example, 10 grams of sugar has 41 Calories.
e m
r i – When 10 grams of sugar are burned, 41 kcal (170 kJ)
of energy is released.
m s
– Your body “burns” food for energy.
o t
r – In order to use the energy available in 10 grams of su
gar, you must do 41 kcal worth of work.
y
ENERGY
 Pharm Chem 11

Thermochemistry
What is ENERGY
 simply defined as the “Ability to do work”
 quantitative property that must be transferred to a body
or physical system to perform work on the body, or
to heat it.
 in the International System of Units (the SI system), the
unit of energy is the Joule (J).
 One kilojoule (kJ) equals 1,000 joules (J) = is the amount of
the heat required to raise the temperature of 239g of water
by 1ºC
 It takes 4.18 joules (J) to raise the temperature of 1 g of wat
er by 1ºC (at a temperature of 25ºC).
 Pharm Chem 11

Thermochemistry
FORMS OF ENERGY
 Energy appears in many forms.
 There are five main forms of energy:
1. Mechanical
 Kinetic
 Potential
2. Chemical
3. Electromagnetic
4. Nuclear
5. Heat (Thermal)
 Pharm Chem 11
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T h KINETIC ENERGY
h e
e m Kinetic Energy
 energy of motion
r i  depends on both mass
m s and velocity
o t  the faster the object
moves - the more kine
r tic energy it have...
y  increases as the motio
n also increases
 Pharm Chem 11

Thermochemistry
KINETIC ENERGY
 Pharm Chem 11
c
T h POTENTIAL ENERGY
h e
e m  the amount of energy
that is stored or in pos
r i ition
m s  increases based on its
o position or height
t
r
y
 Pharm Chem 11

Thermochemistry
CHEMICAL ENERGY
 the energy stored in the bonds
of atoms and molecules release
d by chemical reaction

 this is a form of potential

energy until the bonds
are broken
 Pharm Chem 11
c
T h ELECTROMAGNETIC ENERGY
h e  a form of energy that is reflected or emitt
e m ed from objects in the form of electrical
and magnetic waves that can travel
r i through space
 moving electric charges
m s
 Examples:
o t  Power lines carry electricity
r  Electric motors are driven by electro
magnetic energy
y  Light is this form of energy (X-rays,
radio waves, laser light, etc.)
 Pharm Chem 11

Thermochemistry
NUCLEAR ENERGY
 energy released when th
e nucleus of an atom
splits, nuclear energy is
released.
 Nuclear energy is the
most concentrated form
of energy.
 Fission/Fusion
 Pharm Chem 11
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T h THERMAL ENERGY
h e  this is the internal energy of
e m a substance is determined by
the movement of the molecul
r i es and the potential energy of
m s the arrangement of molecule
s.
o t  also the heat energy when the
molecules move from a warm
r er substance to a colder one
y  the faster the molecules move,
the higher the thermal (heat)
energy
 Pharm Chem 11

Thermochemistry
THERMAL ENERGY
 Temperature is the measure of the average kinetic
energy of the individual molecules of a substance

 Units of Thermal Energy : Joule

 However, sometimes the calorie is used for Heat..

 To convert calories to joules multiply the calories by 4.18.
 To convert joules to calories divide by 4.18
 Pharm Chem 11
c
T h Measuring Thermal Energy
h e  Thermometers are device that is used
to measure kinetic energy not
e m temperature.
r i  Thermometers rely on a simple physic
al property of all substances
m s  MOST OBJECTS EXPAND WHEN
THEIR TEMPERATURE INCREASES
o t  Thermometers use liquids substance
r like mercury and colored alcohol
that expand as their temperatures
y increase and contract as temperature
decreases
 Pharm Chem 11

Thermochemistry
Temperature Scales
Fahrenheit Scale
 Most familiar to you from your friendly weather reports
 Units called DEGREES FAHRENHEIT [ °F]
 Water freezes at 32 °F and Boils at 212 °F

Celsius Scale
 Widely used in science and other countries
 Units called DEGREES CELSIUS [°C]
 Celsius scale is based the values of 0 °C to freezing point
of water and a value of 100 °C to boiling point of water
(at standard pressure)
 Pharm Chem 11
c
T h Temperature Scales
h e Kelvin Scale
e  Based on absolute zero the temperature
m at which an objects energy is minimal
r i  Units called KELVIN [K]
 On the Kelvin scale, Zero (0) Kelvin is
m s absolute zero
o t
r
y
 Pharm Chem 11

Thermochemistry
ENERGY TRANSFER
 energy or heat transfer in every chemical processes occurs in
an invisible area or where it allows its the exchange or transfer,
known as the SYSTEM
 SYSTEM - part of the universe that is of interest
in the study of thermochemistry
and thermodynamics
3 Types of System:
1. OPEN - allows exchange of matter and energy
2. CLOSED - allows exchange of energy only
3. ISOLATED - does not allows exchange of matter and energy
 Pharm Chem 11
c
T h ENERGY TRANSFER
h e
e m
r i
m s
o t
r
y
 Pharm Chem 11

Thermochemistry
Methods of Energy Transfer

 Energy transfer as heat from a hot object can occur in

3 ways:
 Conduction
 Convection
 Radiation
 Heat transfer will stop when thermal equilibrium is re
ached, that is the rate at which energy flows out of a
substance equals the rate that energy flows into the
substance
 Pharm Chem 11

Thermochemistry
Methods of Energy Transfer
CONDUCTION
 the transfer of energy as
heat between particles as
they collide with a substance
or between 2 objects in contact
 Energy transfer through solids
by direct contact
 Example: Heating marshmallows
with a metal rod, as the
marshmallow cook, the wire
you are holding is getting
hotter.
 Pharm Chem 11
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T h Methods of Energy Transfer
h e CONVECTION
 the transfer of energy by the move
e m ment of fluid with different temp
erature
r i  During convection, energy is carri
ed away by a heated gas or liquids
m s that expand and rises above coole
o t r, denser gas or liquid
 Energy transfer through gases and
r liquids (both fluids)
 The cycle of a heated fluid that ris
y es and then cools and fall is called
convection current
 Pharm Chem 11

Thermochemistry
Methods of Energy Transfer
RADIATION
 The transfer of energy by
electromagnetic waves
 Energy transfer that does not
need any material to transfer
to, it travels in waves
 Radiation differs from conduction
and convection in that it does
not involve the movement of matter
 Pharm Chem 11
c
T h INTERNAL ENERGY
h e  relative type of energy
 the total energy attributed to the particles of matt
e m er and their interaction within a system
r i  composed of thermal and chemical energy
 represented by the symbol “U”
m s
o t  the change in internal energy of a system is equal
to the heat added to the system minus the work
r done by the system
y
Thermo
Dynamics
WORK WORK
 Pharm Chem 11

ThermoDYNAMICS
DEFINITION & CONCEPT
 a branch of physics that deals with heat, work, and temperature,
& their relation to energy, radiation, and physical properties of
matter.
 study of the relations between heat, work, temperature, and ener
gy.

 The laws of thermodynamics describe how the energy in a system

changes and whether the system can perform useful work on
its surroundings.
 Pharm Chem 11

d Thermodynamic System
T
y
h
n
e
a
r
m
m
i
o
c
s
 Pharm Chem 11

ThermoDYNAMICS
Thermodynamic System
ENTHALPY ENTROPY
 measure of total heat  the measure of the level of disor
content in a thermodynamic der in a thermodynamic system
system  “degree of disorderliness or
 “Energy of a reaction” randomness”

 denoted by  denoted by symbol

symbol “H” “S”
 Pharm Chem 11

d Thermodynamic System
T
y
h
n
e
a
r
m
m
i
o
c
s
 Pharm Chem 11

ThermoDYNAMICS
Thermodynamic System
 Pharm Chem 11

d Types of process in a Thermodynamic system

T
y
h  It is also known as the reactions in a thermodynamic system
n
e Non –
a Sponta
r capable of sponta
m neous proceeding in a
given direction neous
do require energy input
from its surrounding to
m without needing to
proceed
i be driven by an also called an
o outside source of
endergonic reaction or
an unfavorable reaction
c energy.
also called natural
s processes, proceed
when left to
is a chemical reaction in
which the standard
themselves, and in the change in free energy is
absence of any attempt positive, and energy is
to drive them in absorbed.
reverse.
 Pharm Chem 11

d Thermodynamic system
T
y
h
n
e
a
r
m
m
i
o
c
s
 Pharm Chem 11

ThermoDYNAMICS
Gibb's Free Energy
Enthalpy (H)
 energy of rxn
 -H released heat
 +H absorbed heat

Entropy (S)
 degree of randomness
 -S low deg of randomness
 +S high deg of randomness

G = 0 = rxn is in equilibrium
 Pharm Chem 11

d
T LAWS OF THERMODYNAMICS
y
h
n
e
a
r
m
m
i
o
c
s
 Pharm Chem 11

ThermoDYNAMICS
1ST Law of Thermodyanmics

 “Energy cannot
be created nor
destroyed; it can
only be redistrib
uted or changed
from one form to
another.”
 Pharm Chem 11

d 1st Law of Thermodynamics

T
y
h
n or ΔE= q+w
e
a
r
m
m
i
o
c
s
 Pharm Chem 11

ThermoDYNAMICS
2nd Law of Thermodynamics
 “Entropy of any
isolated system not in
thermal equilibrium alm
ost always increases.”
 Pharm Chem 11

d 3rd Law of Thermodynamics

T
y
h
n
e
a
r
m
m
i  “the entropy of a system approaches a constant
o value as the temperature approches zero.”
c
 if T = O ; S = O for all substances
s
 Pharm Chem 11

ThermoDYNAMICS
ZEROETH of Thermodynamics
 This law was formulated after the enunciation of the first law of
thermodynamics. But, since this law was considered to be of pri
mary importance, it was called zeroeth law.

 States that “if two systems are in thermal equilibrium with a

third system, they are also in equilibrium with each other.”
 Pharm Chem 11

d Zeroth Law of Thermodynamics

T
y
h
n
e
a
r
m
m
i
o
c
s
 Pharm Chem 11

d THERMAL EQUILIBRIUM
T
y
h  important concept related to temperature is thermal
n equilibrium.
e  Two objects are in thermal equilibrium if they are in
a close contact that allows either to gain energy from th
r e other, but nevertheless, no net energy is transferred
m between them.
m  Even when not in contact, they are in thermal equilibri
i
o um if, when they are placed in contact, no net energy
c is transferred between them.
 If two objects remain in contact for a long time, they
s typically come to equilibrium. In other words, two ob
ects in thermal equilibrium do not exchange energy.
 Pharm Chem 11

d THERMAL EQUILIBRIUM
T
y
h  Suppose that a small metal cup of hot water is placed inside of
n a larger Styrofoam cup of cold water. Let's suppose that the
e temperature of the hot water is initially 70°C and that the tem
a perature of the cold water in the outer cup is initially 5°C. And
r let's suppose that both cups are equipped with thermometers (
m or temperature probes) that measure the temperature of the w
m ater in each cup over the course of time. What do you suppose
i will happen?
o  When the cold water is done warming and the hot water is
c done cooling, will their temperatures be the same or differ
ent?
s  Will the cold water warm up to a lower temperature than
the temperature that the hot water cools down to?
 Or as the warming and cooling occurs, will their temperat
ures cross each other?
 Pharm Chem 11

d THERMAL EQUILIBRIUM
T
y
h Hot water
n
e
a
r
m
m
i Thermal equilibrium
o
c
s Cold water