Chemistry for Engineers

Thermochemistry
CHEMISTRY
Chemistry for Engineers FOR ENGINEERS
PAUL JHON G. EUGENIO
Instructor I
Thermochemistry
• A branch of chemistry concerned with the heat
effects that accompany chemical reactions.
Getting Started: Some Terminology
• System – a part of the universe which we are concerned with to be studied

• Surroundings – are the part of universe outside the universe in which the
system interacts.

• Universe= System + Surroundings

Three common systems
• Open system- freely exchanges
matter and energy to the
surroundings.

• Closed system –can exchange

energy, but not matter, into the
surroundings

• Isolated system- neither matter

nor energy interact with the
surroundings
Energy
• Derived from the Greek word which means to
“work within.
-capacity to work
• WORK- is performed when a force acts through
a distance.
Energy can be further characterized as Kinetic
Energy and Potential Energy.
Kinetic Energy vs. Potential Energy
• Kinetic energy is
associated with matter
motion.

• Potential Energy is the

energy resulting from
the position and
composition of matter.
• Kinetic energy associated with random
molecular motion is sometimes called
THERMAL ENERGY.
Heat
• Energy transferred between a
system and its surroundings
as a result of temperature
difference between the two.

• Energy that passes from a

warmer body (with a higher
temperature) to a colder body
(with a lower temperature) is
transferred as heat.
Heat
• In some cases, heat can be
transferred at constant
temperature.
• For example, when a solid is
heated, the molecules or ions
move with greater vigor and
eventually break free from their
neighbors overcoming the
attractive forces between them.
• A process occurring at constant
temperature is said to be
ISOTHERMAL.
Heat Capacity
• Quantity of heat require to change
temperature of a system by one
degrees.

*if the system is a mole of a substance,

molar heat capacity is applicable.

*if the system is a gram of a substance,

the applicable term is specific heat
capacity/specific heat.
Heat Capacity
• The specific heats substances are somewhat
temperature dependent. At 25OC, the specific heat
water is

Cwater=4.18 J/gOC
[The SI unit for heat is simply joule (J) but historically,
it has been called the calorie (cal)]

q=mC∆t
Where q= quantity of heat;m= mass of substance; ∆t=
change in temperature
Calculating a quantity of heat
How much heat is required to raise the
temperature of 7.35 g of water from 21.0OC to
98.0OC? (Assume the specific heat of water is 4.18
J/g OC at this temperature range)

q=mC∆t
q= (7.35 g)(4.18J/g OC)(98OC-21OC)
q=2.36x103 J
Practice Problems
• How much heat in kilojoules (kJ), is required to
raise the temperature of 237g of cold water from
4OC to 37 OC(body temperature)?

• How much heat in kilojoules (kJ), is required to

raise the temperature of 2.50kg of liquid
mercury from -20OC to -6.0OC? (Assume a
density of 13.6 g/mL and a molar heat capacity
of 28.0 J/molOC )
Law of Conservation of Energy
• A positive q signifies that the heat is absorbed or
gained by the system.
• A negative q signifies that the heat is released or
lost by the system.
• Energy is neither created nor destroyed but it is
only transferred from system to surroundings
vice versa. This means that,
q system + q surroundings = 0
q system=- q surroundings
Experimental Determination of Heat
Capacities
(a) A 150.0 g of lead is heated to the temperature
of boiling water (100 OC)
(b) A 50.0 g of sample water is added to thermally
insulated beaker, and its temperature is found to
be 22.0 OC
(c) The hot lead is dumped into the cold water,
and the temperature of the final lead-water
mixture is 28.8 OC
CALCULATE THE SPECIFIC HEAT OF LEAD.
Solution
First calculate the heat absorbed by water using q=mC∆t
q=50.0g(4.18 J/gOC)(28.8-22.0)OC= 1.4x103 J
Then, the absorbed heat by the is equal to the heat
released by lead, that is
qlead=-qwater
qlead=150.0 g x specific heat of lead x (28-100)OC=-
1.4x103 J
Specific heat of lead= 0.13 J/g OC
Practice Problems
• When 1.00kg of lead (specific heat= 0.13 J/gOC)
at 100OC is added to quantity of water 28.5OC,
the final temperature of the lead-water mixture
35.2OC. What is the mass of water present?

• A 100.0 g copper sample (specific heat = 0.385

J/g OC) at 100OC is added to 50.0g water at
26.5OC.What is the final temperature of the
copper-water mixture?
Heats of Reaction and Calorimetry
• In a chemical reaction, a change in the chemical
energy associated with reactants and products
may appear as heat.

• Heat of reaction is defined as the quantity of

heat exchanged between system and its
surroundings when the reaction occurs at
constant temperature.
Heats of Reaction and Calorimetry
• Exothermic reaction – is one that produces a temperature
increases in an isolated/non isolated system, gives off
heat to the surroundings. The heat of reaction is negative
(qrxn<0)

• Endothermic reaction- is the reaction that produces a

temperature decrease in a system, or a gain of heat from
the surroundings. The heat of reaction is positive (qrxn>0).

• Heats of reaction are experimentally determined using a

calorimeter
Calorimetry
• A device used in measuring quantities of heat.

• There are two types of calorimeter namely:

 bomb calorimeter
 “stytofoam cup” calorimeter
Bomb Calorimeter
• Constant volume calorimeter;
the system is isolated from its
surroundings
• This type of calorimeter is
ideally suited for measuring
heat evolved in a combustion
reaction.
• qrxn =-qcalorimeter
• qcalorimeter=(heat capacity of
calorimeter)X ∆t
Using Bomb Calorimetry Data to determine
the heat capacity
• The heat of combustion of benzoic acid is -26.42
kJ/g. The combustion of 1.176g sample of
benzoic acid causes a temperature increase of
4.96OC in a bomb calorimeter assembly. What is
the heat capacity of the assembly?

Answer: 4.52 kJ/OC

Practice Problem
• Vanillin is a natural constituent of vanilla. It is
also manufactured for use in the artificial
flavoring. The combustion 1.103g of vanillin,
C8H8O3, in the same bomb calorimeter in the
example causes the temperature to rise from
24.89OC to 30.09OC. What is the heat of
combustion of vanillin, expressed in kilojoules
per mole?
Styrofoam Cup Calorimeter
• Constant pressure calorimeter
• This type of calorimeter is
usually constructed using
styrofoam cup from the fact the
styrofoams are good heat
insulator so there is a very little
heat transfer between the cup
and the surrounding air.
Using a heat of reaction from Calorimetry
Data
• Neutralization reaction:
H+ + OH- H2O
Two solutions, 25.00mL of 2.50M HCl(aq) and
25.00mL of 2.50M NaOH(both) initially at
21.1OC, are added to styrofoam cup calorimeter
and allowed to react. The temperature rises to
37.8OC. Determine the heat of neutralization
reaction, expressed per mole of H2O Is the
reaction exothermic or endothermic?
Answer
-56 kJ/mol H2O ; exothermic
Practice Problem
• Two solutions, 100.0 mL of 1.00 M AgNO3(aq)
and 100mL of 1.00M NaCl(aq) both initially at
22.4OC, are added to styrofoam cup calorimeter
and allowed to react. The temperature rises to
30.2OC. Determine the qrxn per mole of the
AgCl(s) in the reaction.

Ag+ + Cl- AgCl(s)

Work
• Work involved in the compression or expression
of gases is call pressure-volume work.

• P-V work is the type of work performed by

explosives and by the gases in the combustion of
gasoline in an automobile engine.
• We can calculate the work done by the gas in
moving weight of mass M through displacement
∆h. That is,

work(w)= force (M × g) × distance (∆h)

work(w)=-M × g × ∆h
Or we can say that,
work= -P∆V
First Law of Thermodynamics
• Internal energy (U) is the total energy in a
system. (both kinetic and potential energy)
• A system contains only internal energy. It does
not contain energy in the form of heat and work.
• Heat and work exist only during a change in the
system.
First Law of Thermodynamics
• Moreover, the relationship of internal energy
(U), work (w) and heat (q) is dictated by the Law
of Conservation of Energy, expressed in the form
known as the first law of thermodynamics.

∆U= q+w
*an isolated system is unable to exchange either
heat or work with its surroundings, so that
∆Uisolated system= 0
First Law of Thermodynamics
In using that equation, keep in mind that

• Any energy entering the system carries a positive sign. Thus ,if heat is absorbed
by the system, q>0. If work is done on the system, w>0.

• Any energy leaving the system carries a negative sign. Thus, if heat is given off
by the system, w<0.

• In general, the internal energy of a system changes as a result of energy entering

or leaving the system as heat and/or work. If, on balance, more energy enters
the system than leaves, ∆U is positive. If more energy leaves than enters the
system, ∆U is negative

• A consequence of ∆Uisolated system= 0 is that ∆Usystem= -∆Usurroundings

:that is energy is conserved
Illustration of sign convention used in
thermodynamics
Relating q,w and ∆U
• A gas while expanding, absorbs 25J of heat and
does 243J of work. What is the ∆U of the gas?

Answer: -218J
Practice Problem
• In compressing a gas, 355 J of work is done on
the system. At the same time, 185J of heat
escapes from the system. What is the ∆U of the
system?
State Function vs Path Functions
• State functions
- Any property that has a unique value for a
specified state of a system is said to be state
function.

It depends on the state of the system not on how

that state was established.
How?
• Obtain three samples of water; one purified by
extensive distillation of groundwater; one
synthesized by burning pure hydrogen gas in
pure oxygen gas; one is prepared by driving off
CuSO4.5H2O and the condensing the gaseous
water into liquid
Then?
• The densities of three different samples for the
state specified will be all the same:
0.99820g/mL
State Function vs Path Functions
• Path functions, on the other hand, depend on
the path followed when a system undergoes a
change.
Heats of reaction: ∆U and ∆H
Reactants(initial state) to Product(final state)
∆U= Uf-Ui
Then,
∆U= qrxn+w
Recall that work= -P∆V and in bomb calorimeter
reactants and products are confined in a bomb.
Thus, the volume is constant.
Heats of Reaction ∆U and ∆H
• Since the volume is constant; no work is done.

∆U= qrxn + w = qrxn + 0 = qrxn = qv

Denoting the heat of reaction for a constant
volume reaction as qv

∆U= qv
Heat of Reactions ∆U and ∆H
∆U= qv
In some reactions carried out in a constant pressure;
q v = qp + w
Now using ∆U= qv and w= -P∆U= qv
we obtain,
qp = ∆U + P∆V
Finally we can denote qp as the change in enthalpy as
∆H
So that
∆H= ∆U + P∆V
Remember
Reactions carried out at constant volume,
∆U= qv

Reactions carried out at constant pressure,

∆H= qp
∆U and ∆H changes in a Chemical Reaction

• Consider the following combustion reaction,

C12H22O11 + 12O2 12CO2 + 11H2O
∆H= -5.65 x 103 kJ (exothermic)

How much heat is associated with the complete

combustion of 1.oo kg of sucrose?

Answer: -1.65 x 104 kJ

Practice Problem
• What mass of sucrose must be burned to
produce 1.0o x 103 kJ of heat?
Enthalpy changes accompanying changes in
state of matter
• Calculate the change in enthalpy for the process
in which 50.0 g of water is converted from liquid
to 10.0OC to vapor at 25.0OC?
Specific heat of water= 4.18 J/gOC
Molar enthalpy of vaporization= 44.0 kJ/mol

Answer: ∆H=125kJ (note that the enthalpy is

positive, which reflects that the water gains
energy)
Practice Problem
• What is the enthalpy change when a cube of ice
2.00cm on edge is brought from -10.0OC to a
final temperature of 23.2OC? For ice use density
of 0.917 g/cm3, a specific heat 2.01J/gOC and an
enthalpy of fusion of 6.01 kJ/mol.
Indirect Determination of ∆H: Hess Law
• ∆H is an extensive property: Consider the standard
enthalpy change in the formation of NO(g) from its
elements at 25OC

N2 + O2 2NO ∆HO= 180.50 kJ

To express the enthalpy change in terms of one mole of NO,

we divide the coefficients as well as the enthalpy value by
two:

½ N2+ ½ O2 NO ∆HO= ½ x 180.50 kJ = 90.25kJ

Indirect Determination of ∆H: Hess Law
• ∆H is changes sign when reversed:
N2 + O2 2NO ∆HO= 180.50 kJ

2NO N2 + O2 ∆HO= -180.50 kJ

Indirect Determination of ∆H: Hess Law
• Hess Law of Constant Heat Summation

½ N2(g) + O2(g) NO(g) + ½ O2(g) ∆HO=+90.25kJ

NO(g) + ½ O2(g) NO2(g) ∆HO=-57.07 kJ
½ N2(g) + O2(g) NO2(g) ∆HO=+33.18 kJ
Standard Enthalpies of Formation
• The standard enthalpy of formation ∆Hof of a
substance is the enthalpy change that occurs in
the formation of one mole of a substance in the
standard state from the reference forms of the
elements in their standard states.

The standard enthalpy of formation of a pure

element in its reference form is O
Na(s), H2, N2, O2, C(graphite), Br2 (l)
Relating standard enthalpy of Formation to
Chemical Equation
• The enthalpy of formation of formaldehyde is
∆Hof = -108.6 kJ/mol HCHO(g) at 298 K. Write
the chemical equation in to which the value
applies.
Answer

H2(g) + ½ O2(g) + C(graphite) HCHO (g)

∆Hof = -108.6 kJ/mol

Practice Problems
• The standard enthalpy of formation for the
amino acid leucine is 673.3 kJ/mol C6H13O2N (s).
Write the chemical equation for which the value
applies.
Calculating ∆Ho from tabulated values of
∆Hof
Calculating Unknown ∆Hof value
Thermochemistry
Chemistry for Engineers