Thermochemistry Notes

I. Thermochemistry deals with the

changes in energy that accompany a
chemical reaction. Energy is measured in
a quantity called enthalpy, represented as
H. The change in energy that
accompanies a chemical reaction is
represented as H. Page 519
a. The energy absorbed or released as heat
in a chemical or physical change is
measured in a calorimeter. In one kind of
calorimeter, known quantities of reactants
are sealed in a reaction chamber, which is
immersed in a known quantity of water in
an insulated vessel. Therefore, the energy
given off (or absorbed) during the reaction
is equal to the energy absorbed (or given
off) by the known quantity of water. The
amount of energy is determined from the
temperature change of the known mass of
surrounding water.
Calorimeter
 Using the change in temperature, T,
determined from calorimeter one can
use the following equation to
determine the quantity of energy
gained or lost during the reaction or
for a physical change:
q = (cp)(m)(T)
T in kelvin
q represents the energy lost or gained (in
J)
m is the mass of the sample (in g)
cp is the specific heat of a substance at a
given temperature
pg513
• Practice Problem: 1. How much heat energy
is needed to raise the temperature of a 33.0
gram sample of aluminum from 24.0C to
100.C?
• 2. Determine the specific heat of a material if
a 35 g sample absorbed 96 J as it was heated
from 293K to 313K.
• 3. During a chemical reaction carried out in a
calorimeter the temperature of water within the
calorimeter raised from 24.0C to 125C. If
250. grams of water were present calculate
the amount of heat energy the water gained.
b. In thermochemical equations the
quantity of energy released or absorbed as
heat during a reaction is written and is
represented by H.
Example:
2H2(g) + O2(g)  2H2O(l) H= - 571.6 kJ/mol
c. H can be used to determine if the
reaction is exothermic or endothermic. If
the H value of an equation is negative
that represents an exothermic reaction.
(Meaning energy is released, therefore
the energy of the products would be less.)

If the H value of an equation is positive

that represents an endothermic
reaction. Example:
2H2(g) + O2(g)  2H2O(g)
H= - 483.6 kJ/mol
H reactants = 1450.8 kJ/mol
H products = 967.2 kJ/mol
Type of Reaction: Exothermic
2H2O(g)  2H2(g) + O2(g)
H= + 483.6 kJ/mol
H reactants = 967.2 kJ/mol
H products = 1450.8 kJ/mol
Type of Reaction: Endothermic
d. Hess’s law provides a method for
calculating the H of a reaction from
tabulated data. This law states that if two
or more chemical equations are added,
the H of the individual equations may
also be added to find the H of the final
equation. As an example of how this law
operates, look at the three reactions
below.
(1) 2H2(g) + O2(g)  2H2O(l)H = 571.6 kJ/mol

(2)2H2O2(l)  2H2(g) + 2O2(g)H = +375.6 kJ/mol

(3)2H2O2(l)  2H2O(l) + O2(g)H = ? kJ/mol

When adding equations 1 and 2, the 2 mol of
H2(g) will cancel each other out, while only 1
mol of O2(g) will cancel.

(3)2H2O2(l)  2H2O(l) + O2(g)H = ? kJ/mol

Warm-up
• What type of
energy and energy
transfer do you see
in this picture
•Thank you Ms.
Bouwman (from
McNeil High
School) for this
wonderful power
point!
Basic Thermochemistry

Courtesy of lab-initio.com
Energy is the capacity to do work
• Thermal energy is the energy associated with the random motion of
atoms and molecules
• Chemical energy is the energy stored within the bonds of chemical
substances
• Nuclear energy is the energy stored within the collection of neutrons
and protons in the atom
• Electrical energy is the energy associated with the flow of electrons
• Potential energy is the energy available by virtue of an object’s position

6.1
Energy
Energy is the capacity to do work,
work and can take many
forms
 Potential energy is stored energy or the energy
of position
 Kinetic energy is the energy of motion
 Thermal energy (heat) is an outward
manifestation of movement at the atomic level

Heat (Enthalpy) Change, ΔH

Definition: The amount of heat energy released or
absorbed during a process.
 Energy Changes in Chemical Reactions
Heat is the transfer of thermal energy between two bodies that are
at different temperatures.

Temperature is a measure of the thermal energy.

Temperature = Thermal Energy

900C
400C

greater thermal energy

6.2
Heat Cup gets cooler while
hand gets warmer
The flow of thermal
energy from one object
to another.

Heat always flows

from warmer to
cooler objects.
Ice gets warmer
while hand gets
cooler
 3 Types of Heat Transfer
• Radiation- the transfer of energy by
electromagnetic waves.
• Convection – Transfer of energy by currents
• Conduction – Transfer of energy by touching
objects
Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the
surroundings. 2H (g) + O (g) 2H O (l) + energy
2 2 2

H2O (g) H2O (l) + energy

Endothermic process is any process in which heat has to be

supplied to the system from the surroundings.
energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

6.2
Exothermic Processes
Processes in which energy is released as it proceeds, and
surroundings become warmer

Reactants  Products + energy

 Endothermic Processes
Processes in which energy is absorbed as it proceeds,
and surroundings become colder

Reactants + energy  Products

Water phase changes
Temperature remains constant
__________ during a phase change.
 Phase Change Diagram
Processes occur by addition of energy 
 Processes occur by removal of energy
Thermochemical Calculations
 Units for Measuring Heat
The Joule is the SI system unit for measuring
heat:
2
1 kg  m
1 Joule  1 newton  meter  2
s
The calorie is the heat required to raise the
temperature of 1 gram of water by 1 Celsius
degree

1calorie  4.18 Joules

 Specific Heat

The amount of heat

required to raise the
temperature of one
gram of substance by
one degree Celsius. 6 6
5 5
4 7 4 7
8 8
3 3
2 9 2 9
1 11 1 10
Specific Heat (cp, sometimes s, but usually c)
Things heat up or cool down at different rates.

Land heats up and cools down faster than water, and

aren’t we lucky for that!?
Specific heat is the amount of heat required
to raise the temperature of 1 kg (but in
Chem we use g) of a material by one degree
(C or K, they’re the same size).
Cp water = 4184 J / kg C (“holds” its heat)
Cp sand = 664 J / kg C (less E to change)

This is why land heats up quickly during the day and cools quickly at
night and why water takes longer.
Calculations Involving Specific Heat
Q
Q  m  T  c p OR cp 
m  T
cp = Specific Heat

Q = Heat lost or gained

T = Temperature change

m = Mass
 Specific Heat
The amount of heat required to raise the temperature of one gram
of substance by one degree Celsius.
Substance Specific Heat (J/g·K)
Water (liquid) 4.18
Ethanol (liquid) 2.44
Water (solid) 2.06
Water (vapor) 1.87
Aluminum (solid) 0.897
Carbon (graphite,solid) 0.709
Iron (solid) 0.449
Copper (solid) 0.385
Mercury (liquid) 0.140
Lead (solid) 0.129
Gold (solid) 0.129
The specific heat (s) of a substance is the amount of heat (q) required to raise the
temperature of one gram of the substance by one degree Celsius.

The heat capacity (C) of a substance is the amount of heat

(q) required to raise the temperature of a given quantity
(m) of the substance by one degree Celsius.

C = ms

Heat (q) absorbed or released:

q = mst

q = Ct

t = tfinal - tinitial

6.4
 Specific Heat Capacity

If 25.0 g of Al cool from 310 oC to 37 oC, how many joules of heat

energy are lost by the Al?

heat gain/lose = q = (c)(mass)(∆T)

where ∆T = Tfinal - Tinitial

q = (0.897 J/g•K)(25.0 g)(37 - 310)K
q = - 6120 J

Notice that the negative sign on q signals heat “lost by” or transferred OUT of Al.
How much heat is given off when an 869 g iron bar cools from 94 0C to 50C?

s of Fe = 0.444 J/g • 0C

t = tfinal – tinitial = 50C – 940C = -890C

q = mst = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

6.4
CALORIMETRY
Calorimetry
The amount of heat absorbed or released during a
physical or chemical change can be measured,
usually by the change in temperature of a known
quantity of water in a calorimeter.
calorimeter
 Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0

qrxn = - (qwater + qbomb)

qwater = mst

qbomb = Cbombt

Reaction at Constant V

No heat enters or leaves!

6.4
 Constant-Pressure Calorimetry

qsys = qwater + qcal + qrxn

qsys = 0

qrxn = - (qwater + qcal)

qwater = mst

qcal = Ccalt

Reaction at Constant P

No heat enters or leaves!

6.4
 BOOM! Combustible material ignited at
constant volume! This heats up the
“bomb”, which heats up the water
surrounding it…
First, some heat from reaction warms
the water, which we know the mass
of and “c” for…

qwater = (c)(water mass)(∆T)

THEN, some heat from reaction warms
“bomb,” which has a known specific
heat for the entire apparatus (typically),
so we don’t need the mass…
qbomb = (heat capacity, J/K)(∆T)

Total heat evolved = qtotal = qwater + qbomb

 Practice
A sample of iron metal is added to 75.00 grams of
water originally at 35.0°C in a calorimeter. The final
temperature of the metal and water in the calorimeter
is measured to be 95.0°C.

a) Describe the transfer of heat energy that occurs in

the calorimeter.

(b) Assuming no heat is lost to the outside, how many

joules of heat energy are transferred?
ENTHALPY (H)
 Phase Change Diagram

B
A

E C
 Changing Phase
• Heat of Fusion - heat change for freezing and
melting
• Heat of Vaporization – heat change for condensation
or evaporation
For Water: Heat fusion = 340 J/g Heat vaporization = 2,300 J/g
Heat = (mass)(heat of fusion or vaporization)

How many joules of heat are necessary to melt 500g of

ice at its freezing point?
= 500g * 340J/g
= 170,000 J or 170KJ
Enthalpy (H) is used to quantify the heat flow into or out of
a system in a process that occurs at constant pressure.
H = H (products) – H (reactants)
H = heat given off or absorbed during a reaction

Hproducts < Hreactants Hproducts > Hreactants

H < 0 H > 0 6.3
 ∆Hfo, standard molar enthalpy of formation

∆Hfo = Enthalpy change when 1 mol of compound is formed

from the corresponding elements under standard
conditions

H2(g) + 1/2 O2(g) --> H2O(g)

∆Hfo (H2O, g)= -241.8 kJ/mol
 Decomposition
• ∆Hfo may also be used to calculate the decomposition of
something

• If …
H2(g) + 1/2 O2(g) --> H2O(g) ∆Hf˚ = - 242 kJ/mol

Then…
H2O(g) --> H2(g) + 1/2 O2(g) ∆Hf˚ = + 242 kJ/mol
 Enthalpy Values

• Depend on how the reaction is written and on phases of reactants

and products…
H2(g) + 1/2 O2(g) --> H2O(g)
∆H˚ = -242 kJ
2 H2(g) + O2(g) --> 2 H2O(g)
∆H˚ = -484 kJ
H2O(g) ---> H2(g) + 1/2 O2(g)
∆H˚ = +242 kJ
H2(g) + 1/2 O2(g) --> H2O(liquid)
∆H˚ = -286 kJ
 Huh? So what’s that mean?
To convert 1 mol of water to 1 mol each of
H2 and CO requires 131 kJ of energy.

Since delta H is positive, the “water gas” reaction is

ENDOthermic
6.4
6.5
 A problem… Using Standard Enthalpy
Values
Calculate the heat of combustion of methanol, i.e.,
∆Horxn for
∆Horxn =  ∆Hfo (prod) -  ∆Hfo (react)

CH3OH(g) + 3/2 O2(g) --> CO2(g) + 2 H2O(g)

∆Hfo CH3OH = -238.6 KJ/mol ∆Hfo CO2 = -393.5

∆Hfo O2 = 0 KJ/mol ∆Hfo H2O = -285.8

= -238.6 – (-393.5 + -285.8)

= 442.7 KJ/mol
 Practice
Given the following heats of formation:
NaCl(s): DH(f)= -400 kJ
H2SO4(l): DH(f)= -800 kJ
Na2SO4(s): DH(f)= -1400 kJ
HCl(g): DH(f)= -90 kJ

a) Find the heat of reaction of the following chemical change:

2NaCl(s) + H2SO4 --> Na2SO4(s) + 2HCl(g)

b) Is this reaction exothermic or endothermic?

 Energy Stoichiometry
• Remember…
1. In an equation coefficients mean moles!
2. To go from grams to moles divide by molar mass
3. To go from moles to grams multiply my molar
mass
4. Make sure you use the right energy units KJ vs. J
5. Double check the sign of your energy, is it
endothermic or exothermic
 Practice

How much heat is evolved when 266 g of white phosphorus (P 4) burn in air?

P4 (s) + 5O2 (g) P4O10 (s) H = -3013 kJ

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4
 Practice
The burning of magnesium is a highly
exothermic reaction.
2Mg(s) + O2(g) --> 2MgO(s) + 1500 kJ

Use the thermochemical equation to calculate

the energy change in kilojoules when 0.5 mol of
Mg burn in an excess of O2.
 You try
• Calculate the change in H when 32g of NO
decomposes?
– ½ N2 (g) + ½ O2 (g)  NO (g) ∆Hf˚ = 90.2 kJ
 Using Standard Enthalpy Values
Use ∆H˚’s to calculate enthalpy change for

H2O(g) + C(graphite) --> H2(g) + CO(g)

• When calculating ∆H information from several

equations is needed
 And then…
H2O(g) + C(graphite) --> H2(g) + CO(g)

From either givens within the problem or reference

books and tables we can find…
• H2(g) + 1/2 O2(g) --> H2O(g) ∆Hf˚ = - 242 kJ/mol

• C(s) + 1/2 O2(g) --> CO(g) ∆Hf˚ = - 111 kJ/mol

 And and then… we add ‘em.
H2O(g) --> H2(g) + 1/2 O2(g) ∆Ho = +242 kJ
C(s) + 1/2 O2(g) --> CO(g) ∆Ho = -111 kJ
-----------------------------------------------------------------
-------
H2O(g) + C(graphite) --> H2(g) + CO(g)

∆Honet = +131 kJ
• Positive delta H means?
 Warm-Up
• Calculate the change in H when 64g of NO is
formed?
– ½ N2 (g) + ½ O2 (g)  NO (g) ∆Hf˚ = 90.2 kJ
Enthalpy Day 2
 Things to remember about Thermochemical Equations

1. The coefficients always refer to the number of moles of a

substance
H2O (s) H2O (l) H = 6.01 kJ

2. If you reverse a reaction, the sign of H changes

H2O (l) H2O (s) H = -6.01 kJ

3. If you multiply both sides of the equation by a factor n, then H

must change by the same factor n.

2H2O (s) 2H2O (l) H = 2 x 6.01 = 12.0 kJ

6.3
 Thermochemical Equations

4. The physical states of all reactants and products must be

specified in thermochemical equations.
H2O (s) H2O (l) H = 6.01 kJ

H2O (l) H2O (g) H = 44.0 kJ

6.3
 What if you have limited information?
Calculate the enthalpy of the reaction:
2 NO(g) + O2(g) --> 2 NO2(g)

Given the following reactions and enthalpies of formation:

½ N2(g) + O2(g) --> NO2(g) ∆ H = 33.2 kJ
½ N2(g) + ½ O2(g) --> NO(g) ∆ H = 90.2 kJ

2 NO(g) + O2(g) --> 2 NO2(g)

2/2 N2(g) + 2 O2(g) --> 2 NO2(g) ∆ H = 33.2 kJ *2
2 NO(g) --> 2/2 N2(g) + 2/2 O2(g) ∆ H = -+90.2 kJ * 2
-114 kJ
 You try…
Calculate the enthalpy of the reaction: 4B(s)
+3O2(g) --> 2B2O3(s)

Given the following information:

B2O3(s) + 3H2O(g) --> 3O2(g) + B2H6(g) ∆ H = +2035 kJ
2B(s) + 3H2(g) --> B2H6(g) ∆ H = +36 kJ
H2(g) + ½ O2(g) --> H2O(l) ∆ H = -285 kJ
H2O(l) --> H2O(g) ∆ H = +44 kJ
 Equilibrium
and
Le Chatelier’s Principle
Chemical Equilibrium
Reversible Reactions:
A chemical reaction in which the
products can react to re-form the
reactants
Chemical Equilibrium:
When the rate of the forward reaction
equals the rate of the reverse reaction
and the concentration of products and
reactants remains unchanged

2HgO(s)  2Hg(l) + O2(g)

Arrows going both directions (  ) indicates equilibrium in a chemical equation
 LeChatelier’s Principle
When a system at Henry Le Chatelier

equilibrium is placed under

stress, the system will
undergo a change in such
a way as to relieve that
stress.
Le Chatelier Translated:
When you take something away from a system at
equilibrium, the system shifts in such a way as to
replace what you’ve taken away.

When you add something to a system at

equilibrium, the system shifts in such a way as to
use up what you’ve added.
 LeChatelier Example #1
A closed container of ice and water at
equilibrium. The temperature is raised.

Ice + Energy  Water

right
The equilibrium of the system shifts to the _______
to use up the added energy.
 LeChatelier Example #2
A closed container of N2O4 and NO2 at equilibrium.
NO2 is added to the container.

N2O4 (g) + Energy  2 NO2 (g)

The equilibrium of the system shifts to the

left to use up the added NO2.
_______
 LeChatelier Example #3
A closed container of water and its vapor at equilibrium.
Vapor is removed from the system.

water + Energy  vapor

The equilibrium of the system shifts to the

right to replace the vapor.
_______
 LeChatelier Example #4
A closed container of N2O4 and NO2 at equilibrium.
The pressure is increased.

N2O4 (g) + Energy  2 NO2 (g)

The equilibrium of the system shifts to the

left
_______ to lower the pressure, because there
are fewer moles of gas on that side of the
equation.
 What about this?
3 H2(g) + N2(g) <--> 2 NH3(g)

What happens when…

a)More N2 is added right/left/no change
b)Pressure is increased right/left/no change
c) Temp. is deceased right/left/no change
 Or this?

• The system depicted here is maintained at a temperature of

30 °C. If the temperature of the system is doubled, the system
will achieve equilibrium by which of the following responses?

a) The temperature of the liquid water will exceed the temperature of

the vapor.
b)  The temperature of the vapor will exceed the temperature of the
liquid water.
c)  A higher percentage of the water vapor in the container will
condense to liquid.
d)   A higher percentage of the water will move into the vapor phase.