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Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.;


and Bruce E. Bursten

Thermochemistry

Thermochemistry
Energy

• The ability to do work or transfer heat.


Work: Energy used to cause an object that
has mass to move.
Heat: Energy used to cause the
temperature of an object to rise.

Thermochemistry
Potential Energy

Energy an object possesses by virtue of its


position or chemical composition.

Thermochemistry
Electrostatic PE
Arises from the interaction between charged
particles.
Eel = k Q1 Q2 k = 8.99x109 Jm/C2
d Q charge of particles
d distance
If charges are same sign they repel and Eel is
positive. If they have opposite sign they
attract and Eel is negative.
The lower the energy of system the more stable
it is. Thus the more strongly opposite charged
Thermochemistry
particles attract each other.
Kinetic Energy

Energy an object possesses by virtue of its


motion.
1
KE =  mv2
2

Thermochemistry
Units of Energy

• The SI unit of energy is the joule (J).


kg m2
1 J = 1 
s2
• An older, non-SI unit is still in
widespread use: The calorie (cal).
1 cal = 4.184 J

Thermochemistry
Joule

• A mass of 2 kg moving at a speed of 1


m/s possesses a kinetic energy of 1 J.

calorie: the amount of heat needed to


increase the temperature of 1 g of water
from 14.5 0C to 15.5 0C.
• 1 Cal = 1000 cal = 1 kcal
Thermochemistry
System and Surroundings
• Consider the reaction inside
the piston
• 2H2(g) +O2->2H2O(g)+heat
• The system includes the
molecules we want to study
(here, the hydrogen and
oxygen molecules).
Reactants an products.
• The surroundings are
everything else (here, the
cylinder and piston). Thermochemistry
Work

• Energy is used to
move an object over
some distance.
• w = F  d,
where w is work, F
is the force, and d is
the distance over
which the force is
exerted.
Thermochemistry
Heat
• Energy can also be
transferred as heat.
• Heat flows from warmer
objects to cooler objects.
• HEAT THE ENERGY
TRANSFERRED
BETWEEN A SYSTEM
AND ITS
SURROUNDINGS AS A
RESULT OF THEIR
DIFFERENCE IN
TEMPERATURE
Thermochemistry
Transferal of Energy

a) The potential energy of this ball of


clay is increased when it is moved
from the ground to the top of the wall.

Thermochemistry
Transferal of Energy

a) The potential energy of this ball of


clay is increased when it is moved
from the ground to the top of the wall.
b) As the ball falls, its potential energy is
converted to kinetic energy.

Thermochemistry
Transferal of Energy

a) The potential energy of this ball of


clay is increased when it is moved
from the ground to the top of the wall.
b) As the ball falls, its potential energy is
converted to kinetic energy.
c) When it hits the ground, its kinetic
energy falls to zero (since it is no
longer moving); some of the energy
does work on the ball, the rest is
dissipated as heat. Thermochemistry
First Law of Thermodynamics
• Energy is neither created nor destroyed.
• In other words, the total energy of the universe is
a constant; if the system loses energy, it must be
gained by the surroundings, and vice versa.

Use Fig. 5.5

Thermochemistry
Internal Energy
The internal energy of a system is the sum of all
kinetic and potential energies of all components
of the system; we call it E.

Use Fig. 5.5

Thermochemistry
Internal Energy
By definition, the change in internal energy, E,
is the final energy of the system minus the initial
energy of the system:
E = Efinal − Einitial

Use Fig. 5.5

Thermochemistry
Changes in Internal Energy

• If E > 0, Efinal > Einitial


Therefore, the system
absorbed energy from
the surroundings.

Thermochemistry
Changes in Internal Energy

• If E < 0, Efinal < Einitial


Therefore, the system
released energy to the
surroundings.

Thermochemistry
Changes in Internal Energy

• When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is, E = q + w.

Thermochemistry
E, q, w, and Their Signs

Thermochemistry
Exchange of Heat between
System and Surroundings
• When heat is absorbed by the system from
the surroundings, the process is endothermic.

Thermochemistry
Exchange of Heat between
System and Surroundings
• When heat is absorbed by the system from
the surroundings, the process is endothermic.
• When heat is released by the system to the
surroundings, the process is exothermic.

Thermochemistry
State Functions
Usually we have no way of knowing the
internal energy of a system; finding that value
is simply too complex a problem.

Thermochemistry
State Functions
• However, we do know that the internal energy
of a system is independent of the path by
which the system achieved that state.
 In the system below, the water could have reached
room temperature from either direction.

Thermochemistry
State Functions
• Therefore, internal energy is a state function.
• It depends only on the present state of the
system, not on the path by which the
system arrived at that state.
• And so, E depends only on Einitial and Efinal.

Thermochemistry
Work

PV work is the work


associated with a
change of
volume ( V) that
occurs against a
resisting pressure.

Thermochemistry
Work
We can measure the work done by the gas if
the reaction is done in a vessel that has been
fitted with a piston.
w = −PV

Thermochemistry
Enthalpy
• If a process takes place at constant
pressure (as the majority of processes we
study do) and the only work done is this
pressure-volume work, we can account for
heat flow during the process by measuring
the enthalpy of the system.
• Enthalpy is the internal energy plus the
product of pressure and volume:
H = E + PV Thermochemistry
Enthalpy

• When the system changes at constant


pressure, the change in enthalpy, H, is
H = (E + PV)
• This can be written
H = E + PV

Thermochemistry
Enthalpy
• Since E = q + w and w = −PV, we
can substitute these into the enthalpy
expression:
H = E + PV
H = (q+w) − w
H = q
• So, at constant pressure the change in
enthalpy is the heat gained or lost.
Thermochemistry
Endothermicity and
Exothermicity
• A process is
endothermic, then,
when H is
positive.

Thermochemistry
Endothermicity and
Exothermicity
• A process is
endothermic when
H is positive.
• A process is
exothermic when
H is negative.

Thermochemistry
Enthalpies of Reaction

The change in
enthalpy, H, is the
enthalpy of the
products minus the
enthalpy of the
reactants:

H = Hproducts − Hreactants
Thermochemistry
Enthalpies of Reaction

This quantity, H, is called the enthalpy of


reaction, or the heat of reaction.

Thermochemistry
The Truth about Enthalpy

1. Enthalpy is an extensive property.


2. H for a reaction in the forward
direction is equal in size, but opposite
in sign, to H for the reverse reaction.
3. H for a reaction depends on the state
of the products and the state of the
reactants.
Thermochemistry
Practice problem– Change in enthalpy – Heat of reaction
3CuCl2 + 2Al  3Cu + 2AlCl3 ΔH = -793.5 kJ

1. What is ΔH for the following reaction?


6CuCl2 + 4Al  6Cu + 4AlCl3

2. What is ΔH for the following reaction?


9 Cu + 6 AlCl3  9 CuCl2 + 6 Al
3. Given the equation at the top of the page, how much energy
will be given off by the reaction of 2.07 g of Al with excess
CuCl2? Thermochemistry
Constant Pressure Calorimetry
By carrying out a
reaction in aqueous
solution in a simple
calorimeter such as this
one, one can indirectly
measure the heat
change for the system
by measuring the heat
change for the water in
the calorimeter.
Thermochemistry
Heat Capacity and Specific Heat
• Calorimeter = apparatus that measures heat flow.
• Heat capacity = the amount of energy required to raise
the temperature of an object (by one degree). (J °C-1)
• Molar heat capacity = heat capacity of 1 mol of a
substance. (J mol-1 °C-1)
• Specific heat = specific heat capacity = heat capacity of 1
g of a substance. (J g-1 °C-1)

q  specific heat  grams of substance  T


Thermochemistry
• Remember a change in T in K and in 0C
are equal in magnitude
• T in K = T in 0C

Thermochemistry
Molar heat capacity

• The heat capacity of one mole of


substance. The amount of heat required
to increase the temperature of 1 mole of
substance 1 K.

Thermochemistry
Constant Pressure Calorimetry
• Atmospheric pressure is constant!

mCT  mCT
Object 1 Object 2
H  qP
qrxn  qsoln  specific heat of solution 
 grams of solution   T
• HEAT LOST = HEAT GAINED

Thermochemistry
Constant Pressure Calorimetry

Because the specific


heat for water is well
known (4.184 J/mol-K),
we can measure H for
the reaction with this
equation:
q = m  s  T

Thermochemistry
Heat Capacity and Specific Heat

Specific heat, then, is


heat transferred
Specific heat =
mass  temperature change
q
s=
m  T

Thermochemistry
Sample problem 1

Find the specific heat of water if


209 J is required to increased the
temperature of 50.0 g of water by
1.00K
s=q / m  T

Thermochemistry
Sample Problem 2

• How much heat is needed to warm


250g of water from 25 0C to 75 0C.
• Specific heat of water 4.18 J/gK
• Find the molar heat capacity of water.

Thermochemistry
Sample problem 3

25.0 mL of 0.100 M NaOH is mixed with 25.0 mL of


0.100 M HNO3, and the temperature of the mixture
increases from 23.1°C to 49.8°C. Calculate ΔH for
this reaction in kJ mol-1. Assume that the specific heat
of each solution is equal to the specific heat of water,
4.184 J g-1 °C-1.

Thermochemistry
Sample problem 4
An unknown metal is to be analyzed for specific heat.
A 12.84-g piece of the metal is placed in boiling
water at 101.5°C until it attained that temperature.
The metal is then removed from the boiling water
and placed into a styrofoam cup containing 54.92 g
of water at 23.2°C. The final temperature of the
water was 26.1°C. What is the specific heat of the
metal sample, in J g-1 °C-1?

Thermochemistry
Bomb Calorimetry

A more
sophisticated model
is the bomb
calorimeter, it has a
chamber where a
chemical reaction
takes place and a
device to start the
reaction.
Thermochemistry
HEAT CAPACITY OF THE
CALORIMETER

• Heat is released when combustion occurs.


The heat is absorbed by the calorimeter and
the T of the water rises.
• THE HEAT CAPACITY OF THE
CALORIMETER HAS TO BE CALCULATED.
It is done by measuring  T in a reaction that
releases a known amount of heat. The heat
capacity of the calorimeter Ccal= amount of heat
absorbed /  T
Thermochemistry
Bomb Calorimetry (Constant Volume Calorimetry)

• Reaction carried out under


constant volume.
• Use a bomb calorimeter.
• Usually study combustion.

qrxn  Ccal  T

Thermochemistry
Bomb Calorimetry

• Because the volume in the bomb calorimeter


is constant, what is measured is really the
change in internal energy, E, not H.
• For most reactions, the difference is very
small.

Thermochemistry
Sample problem 5
A 0.5269 g sample of octane is placed in a bomb
calorimeter with a heat capacity of 11.3 kJ °C-1.
The original temperature of the water in the
calorimeter is 21.93°C. After combustion, the
temperature increases to 24.21°C. Determine the
enthalpy of combustion per mole and per gram of
octane.

Thermochemistry
Sample problem 6
• After 50 mL of 1.0 M HCl and 50mL of 1.0M
NaOH are mixed in a coffe cup calorimeter, the
temperature of the solution increases form 21.0
0C to 27.5 0C. Calculate the enthalpy change for

the rx in kJ/mol of HCl assuming that the


calorimeter loses only a negligible quantity of
heat, total volume of solution is 100mL, that its
density is 1.0 g/mL and the specific heat is
4.18J/gk

Thermochemistry
Hess’s Law

 H is well known for many reactions,


and it is inconvenient to measure H
for every reaction in which we are
interested.
• However, we can estimate H using
H values that are published and the
properties of enthalpy.
Thermochemistry
Hess’s Law

Hess’s law states that


“If a reaction is carried
out in a series of
steps, H for the
overall reaction will be
equal to the sum of
the enthalpy changes
for the individual
steps.”
Thermochemistry
Hess’s Law

Because H is a state
function, the total
enthalpy change
depends only on the
initial state of the
reactants and the final
state of the products.

Thermochemistry
Example
The bombardier beetle uses an explosive discharge as
a defensive measure. The chemical reaction
involved is the oxidation of hydroquinone by
hydrogen peroxide to produce quinone and water:
C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2 H2O (l)

Thermochemistry
C6H4(OH)2 (aq)  C6H4O2 (aq) + H2 (g) ΔH = +177.4 kJ
H2 (g) + O2 (g)  H2O2 (aq) ΔH = -191.2 kJ
H2 (g) + ½ O2 (g)  H2O (g) ΔH = -241.8 kJ
H2O (g)  H2O (l) ΔH = -43.8 kJ

C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2 H2O (l)


ΔH = ???

Thermochemistry
Enthalpies of Formation

An enthalpy of formation, Hf, is defined


as the enthalpy change for the reaction
in which a compound is made from its
constituent elements in their elemental
forms.

Thermochemistry
• Hof .
• Standard conditions (standard state): 1 atm and 25 oC
(298 K).
• Standard enthalpy, Ho, is the enthalpy measured when
everything is in its standard state.
• Standard enthalpy of formation: 1 mol of compound is
formed from substances in their standard states.
• If there is more than one state for a substance under
standard conditions, the more stable one is used.
• Standard enthalpy of formation of the most
stable form of an element is zero.
Thermochemistry
Enthalpies of Formation

Thermochemistry
CONVENTIONAL DEFINITIONS OF
STANDARD STATES FOR
ELEMENTS
• Is the form in which the element exist
under conditions of 1 atm and 25 C.
• For O2 is gas.
• For Na is solid
• For Hg is liquid
• For C is graphite
• By definition the H of formation of the
most stable form of an element is zero.Thermochemistry
Examples – write formation reactions for each:
1. H2SO4
2. C2H5OH
3. NH4NO3

Thermochemistry
Examples
Use the tables in the back of your book to calculate
ΔH for the following reactions:
1. 4 CuO (s)  2 Cu2O (s) + O2 (g)
2. C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
3. NH3 (g) + HCl (g)  NH4Cl (s)

Thermochemistry
Using Enthalpies of Formation of Calculate
Enthalpies of Reaction
• We use Hess’ Law to calculate enthalpies of a reaction
from enthalpies of formation.

Thermochemistry
Using Enthalpies of Formation of Calculate
Enthalpies of Reaction
• For a reaction

H rxn   nH f products    mH f reactants 

Thermochemistry
Calculation of H

We can use Hess’s law in this way:

H =  n Hf(products)
 -  m Hf(reactants)

where n and m are the stoichiometric


coefficients.

Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:

C3H8 (g)  3 C(graphite) + 4 H2 (g)


3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)

Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:

C3H8 (g)  3 C(graphite) + 4 H2 (g)


3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)

Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:

C3H8 (g)  3 C(graphite) + 4 H2 (g)


3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)

Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• The sum of these
equations is:

C3H8 (g)  3 C(graphite) + 4 H2 (g)


3 C(graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)

C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)

Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
H = [3(-393.5 kJ) + 4(-285.8 kJ)] - [1(-103.85 kJ) + 5(0 kJ)]
= [(-1180.5 kJ) + (-1143.2 kJ)] - [(-103.85 kJ) + (0 kJ)]
= (-2323.7 kJ) - (-103.85 kJ)
= -2219.9 kJ

Thermochemistry
Energy in Foods
Most of the fuel in the
food we eat comes
from carbohydrates
and fats.

Thermochemistry
Fuels

The vast majority


of the energy
consumed in this
country comes
from fossil fuels.

Thermochemistry
HW

• PRELAB FOR HESS LAW LAB DUE


TOMORROW (Lab 6 – page 25)
• Remember test on monday
• Hw for Thursday up to 5.77 odd

Thermochemistry
Example
Calculate the total energy produced from the
combustion of one gram of gasoline (assume it is pure
octane, C8H18). Compare that to the energy produced
from the combustion of one gram of ethanol (a
renewable fuel – C2H5OH)

Thermochemistry
• Hess’s law: if a reaction is carried out in a number of
steps, H for the overall reaction is the sum of H for
each individual step.
• For example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = -802 kJ
2H2O(g)  2H2O(l) H = -88 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)H = -890 kJ

Thermochemistry
Note that:
H1 = H2 + H3

Thermochemistry
Foods
• Fuel value = energy released when 1 g of substance is
burned.
• 1 nutritional Calorie, 1 Cal = 1000 cal = 1 kcal.
• Energy in our bodies comes from carbohydrates and fats
(mostly).
• Intestines: carbohydrates converted into glucose:
C6H12O6 + 6O2  6CO2 + 6H2O, H = -2816 kJ
• Fats break down as follows:
2C57H110O6 + 163O2  114CO2 + 110H2O, H = -75,520 kJ
• Fats: contain more energy; are not water soluble, so are
good for energy storage.

Thermochemistry
Fuels
• In 2000 the United States consumed 1.03  1017 kJ of
fuel.
• Most from petroleum and natural gas.
• Remainder from coal, nuclear, and hydroelectric.
• Fossil fuels are not renewable.

Thermochemistry
Sources of
energy
consumed in
USA

Thermochemistry