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Thermochemistry
Thermochemistry
Energy
Thermochemistry
Potential Energy
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
Thermochemistry
Units of Energy
Thermochemistry
Joule
• 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
Thermochemistry
Transferal of Energy
Thermochemistry
Transferal of Energy
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.
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
Thermochemistry
Changes in Internal Energy
Thermochemistry
Changes in Internal Energy
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
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 = −PV
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
Thermochemistry
Enthalpy
• Since E = q + w and w = −PV, we
can substitute these into the enthalpy
expression:
H = E + PV
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
Thermochemistry
The Truth about Enthalpy
Thermochemistry
Molar heat capacity
Thermochemistry
Constant Pressure Calorimetry
• Atmospheric pressure is constant!
mCT mCT
Object 1 Object 2
H qP
qrxn qsoln specific heat of solution
grams of solution T
• HEAT LOST = HEAT GAINED
Thermochemistry
Constant Pressure Calorimetry
Thermochemistry
Heat Capacity and Specific Heat
Thermochemistry
Sample problem 1
Thermochemistry
Sample Problem 2
Thermochemistry
Sample problem 3
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
qrxn Ccal T
Thermochemistry
Bomb Calorimetry
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
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
Thermochemistry
Enthalpies of Formation
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
Thermochemistry
Calculation of H
H = n Hf(products)
- m Hf(reactants)
Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:
Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:
Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in 3 steps:
Thermochemistry
Calculation of H
C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)
• The sum of these
equations is:
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
Thermochemistry
HW
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