-= GNCHM2 S02E01 =-  Temperature is not the measurement of

the thermal energy

THERMOCHEMISTRY  depends on quantity: Extensive property

HEAT
Nature of Heat and thermal energy are different.
Energy  Heat is the transfer of thermal energy
Energy affects matter. between two bodies that are at different
Energy is the capacity to do work. temperatures.
 Work is a force acting over a distance.  Heat flows from warmer objects to cooler
 Energy = work = force × distance objects.
 Energy can be exchanged between objects
through contact (ex. Collisions) Thermochemistry is the study of heat changes
in chemical reactions.
Energy is a quantity an object (or collection of
objects) can possess.
Chemical Energy
Heat and work are two different ways related
It is stored within the structural units of
to how an object can exchange energy with
chemical substances. (It’s a kind of potential
other objects – either out of it, or into it.
energy)
When substances participate in chemical
ENERGY, HEAT, AND WORK
reactions, chemical energy is released, stored,
In Chemistry, work pertains to the directed
or converted to other form of energies.
energy change resulting from a process.
Energy used to cause the temperature of an
Potential Energy
object to rise is called heat.
The energy an object has by virtue of its
position in a field of force, such as
Chemists are interested in different kind of
gravitational, electric or magnetic field.
energies:
𝑃𝐸=𝑚𝑔ℎ
1. Kinetic Energy
m = mass (kg)
2. Radiant Energy
g = gravitational constant (9.80 m/s2)
3. Thermal Energy
h = height (m)
4. Chemical Energy
5. Potential Energy
The SI unit of energy is joule, J.

Kinetic Energy 𝑘𝑔∙𝑚2

J=
The energy associated with an object by virtue 𝑠2
of its motion.
1 The calorie is a non-SI unit of energy
𝐾𝐸 = 𝑚𝑣 2
2 commonly used by chemists. It was originally
m = mass (kg) defined as the amount of energy required to
v = velocity (m/s) raise the temperature of one gram of water by
Thermal energy is a kind of kinetic energy. one degree Celsius.
1 cal = 4.184 J (exact)
Radiant Energy
This energy comes from the sun.
Themodynamic
 Primary energy source for Earth
 Heats the atmosphere and surface of System and
Earth Surroundings
Thermodynamic System
Thermal Energy The substance under study in which a change
Energy associated with the random motion of occurs is called the thermodynamic system (or
atoms and molecules just system).
Thermodynamic Surroundings and final conditions, not on the
Everything else in the vicinity is called the process used.
thermodynamic surroundings (or just the  E = Efinal – Einitial
surroundings).  Ereaction = Eproducts – Ereactants

THREE TYPES OF SYSTEM State Function

1. Open System: Can exchange mass and State functions are the properties that are
heat with surroundings (in the form of determined by the state of system, regardless
heat). e.g. water in an open container. of how that condition was achieved.
2. Closed System: Only transfer of  Energy, pressure, volume, and
energy, not mass. e.g. water in a temperature are the examples of State
closed container. functions.
3. Isolated System: No transfer of mass
or energy. e.g. water in a insulted In the system depicted in this figure, the water
container. could have reached room temperature from
either direction.
Exchange of Energy
1. Energy cannot be created nor
destroyed.
2. Energy can be exchanged between
objects.
3. Energy can also be transformed from
 Internal energy is a state function.
one form to another. (heat → light →
 It depends only on the present state of the
sound)
system, not on the path by which the
system arrived at that state.
First Law of  And so, E depends only on Einitial and Efinal.
Thermodynamics
Law of Conservation of Energy Energy Diagram
 When energy is exchanged between Energy diagrams are a “graphical” way of
objects or transformed into another form, showing the direction of energy flow during a
all energy involved still remains. process.
 The total amount of energy in the universe  If the final condition has a larger amount
before the change has to be equal to the of internal energy than the initial
total amount of energy in the universe condition, the change in the internal
after. energy will be +.
 You can, therefore, never design a  If the final condition has a smaller amount
system that will continue to produce of internal energy than the initial
energy without some source of energy. condition, the change in the internal
energy will be -.
Internal Energy
The internal energy is the total amount of
kinetic and potential energy a system
possesses.
 The change in the internal energy of a
system depends only on the amount of
energy in the system at the beginning and
end.
 A state function is a mathematical function
whose result depends only on the initial
Energy Flow Endothermic vs Exothermic
When energy flows out of a system, it must all Endothermic Process
flow into the surroundings. A chemical reaction or process in which heat
 When energy flows out of a system, is absorbed by the system (q is positive). The
Esystem is -. reaction vessel will feel cool.
 When energy flows into the surroundings,
Esurroundings is +. Exothermic Process
Therefore: A chemical reaction or process in which heat
- Esystem = Esurroundings is evolved by the system (q is negative). The
reaction vessel will feel warm.
When energy flows into a system, it must all
come from the surroundings. In an endothermic reaction:
 When energy flows into a system, Esystem  The reaction vessel cools.
is +.  Heat is absorbed.
 When energy flows out of the  Energy is added to the system.
surroundings, Esurroundings is -.  q is positive.
Therefore: In an exothermic reaction:
Esystem = - Esurroundings  The reaction vessel warms.
 Heat is evolved.
 Energy is subtracted from the system.
 q is negative.

Examples:
1. Chemical heat packs contain iron
filings that are oxidized in an
exothermic reaction. Your hands get
warm because the released heat of the
Energy Exchange reaction is absorbed by your hands.
Energy is exchanged between the system and 2. Chemical cold packs contain NH4NO3
surroundings through heat and work. that dissolves in water in an
 q = heat (thermal) energy endothermic process. Your hands get
 w = work energy cold because they are giving away your
 q and w are NOT state functions; their heat to the reaction.
value depends on the process.
E = q + w Pressure-Volume Work
PV work is work that is the result of a volume
change against an external pressure.
 When gases expand, V is +, but the
system is doing work on the surroundings,
so wgas is -.
 As long as the external pressure is kept
Energy is exchanged between the system and constant
surroundings through either heat exchange or
work being done. - work = external pressure × change in volume;
w = - P V

To convert the units

to joules:
101.3 J = 1 atm∙L.
If a process takes place at constant pressure When a system absorbs heat, its temperature
(as the majority of processes we study do) and increases.
the only work done is this pressure–volume  The increase in temperature is directly
work, we can account for heat flow during the proportional to the amount of heat
process by measuring the enthalpy of the absorbed.
system.  The proportionality constant is called the
 Enthalpy is the internal energy plus the heat capacity, C.
product of pressure and volume:  Units of C are J/°C or J/K.
H = E + PV q = C × T
When the system changes at constant The heat capacity of an object depends on its
pressure, the change in enthalpy, H, is mass.
H = (E + PV)  200 g of water requires twice as much
This can be written heat to raise its temperature by 1 °C as
H = E + PV does 100 g of water.
The heat capacity of an object depends on the
Since E = q + w and w = −PV, we can type of material.
substitute these into the enthalpy expression:  1000 J of heat energy will raise the
H = E + PV temperature of 100 g of sand 12 °C,
H = (q + w) − w but only raise the temperature of 100
H = q g of water by 2.4 °C.
So, at constant pressure, the change in
enthalpy is the heat gained or lost. Specific Heat Capacity
Specific Heat is the measure of a substance’s
Enthalpy of Reaction intrinsic ability to absorb heat
The change in enthalpy, H,  The specific heat capacity is the amount of
is the enthalpy of the heat energy required to raise the
products minus the enthalpy temperature of 1gram of a substance 1 °C.
of the reactants:  Cs
H = Hproducts − Hreactants  units are J/(g∙°C)

The molar heat capacity is the amount of heat

1. Enthalpy is an extensive property. energy required to raise the temperature of
2. H for a reaction in the forward one mole of a substance 1 °C.
direction is equal in size, but opposite
Quantifying Heat Energy
in sign, to H for the reverse reaction.
The heat capacity of an object is proportional
3. H for a reaction depends on the state
to its mass and the specific heat of the
of the products and the state of the
material.
reactants.
So we can calculate the quantity of heat
absorbed by an object if we know the mass,
Calorimetry
the specific heat, and the temperature change
Since we cannot know the exact enthalpy of
of the object.
the reactants and products, we measure H
heat = (mass) × (specific heat capacity) × (temp. change)
through calorimetry, the measurement of q = (m) × (Cs) × (T)
heat flow. Thus,
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 Because H is a state function, the total
the calorimeter. enthalpy change depends only on the initial
state of the reactants and the final state of the
products.
Because the specific heat for water is well
known (4.184 J/g-K), we can measure H for Enthalpies of Formation
the reaction with this equation: An enthalpy of formation, Hf, is defined as
q = m  Cs  T the enthalpy change for the reaction in which
a compound is made from its constituent
elements in their elemental forms.
Bomb Calorimetry
Reactions can be carried Standard enthalpies of formation, Hf°, are
out in a sealed “bomb” measured under standard conditions (25 °C
such as this one. and 1.00 atm pressure).
The heat absorbed (or
released) by the water is We can use Hess’s law in this way:
a very good H = nHf,products – mHf°,reactants
approximation of the where n and m are the stoichiometric
enthalpy change for the coefficients.
reaction.

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.

Hess 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 published
H values and the properties of enthalpy.

Hess’s law states that “if a reaction is carried

“a short 20 min interaction with a therapy dog improved
out in a series of steps, H for the overall student well-being and mood and decreased anxiety levels
reaction will be equal to the sum of the (potentially removing impediments to learning).”

enthalpy changes for the individual steps.” Grajfoner, D., Harte, E. Potter, M. and Mcguigan, N.,
(2017). The Effect of Dog-Assisted Intervention on
Student Well-Being, Mood, and Anxiety. Int. J.
Environ. Res. Public Health 2017, 14(5), 483;
doi:10.3390/ijerph14050483