NATURE OF ENERGY

THERMOCHEMIS
CLASSIFICATION OF ENERGY
TRY  KINETIC ENERGY - Energy of motion or energy that is
A BRANCH OF THERMODYNAMICS THAT being transferred. The energy of an object or a system's
DEALS WITH THE HEAT FLOW THAT particles in motion. (Note: Thermal energy is kinetic energy
ACCOMPANIES CHEMICAL REACTIONS due to the movement of particles)
 POTENTIAL ENERGY – Energy that is stored in an object,
WHAT’S THERMODYNAMICS? or energy associated with the composition and position of
A SCIENTIFIC STUDY OF THE the object. (Note: It is when energy is stored in the structure
TRANSFORMATIONS OF ENERGY.
IT DEALS WITH THE CONCEPTS OF HEAT
of a compound.)
AND TEMPERATURE AND THE INTER-  DIFFERENCE BETWEEN KINETIC AND
CONVERSION OF HEAT AND OTHER FORMS POTENTIAN ENERGY - Kinetic energy is a form of
OF ENERGY. energy possessed by an object due to its motion. In
contrast, Potential energy is defined as the stored form of
energy due to its position. Kinetic energy can be
transferred from one body to another, whereas potential
LAWS OF THERMODYNAMICS
energy is non-transferable.
UNITS OF ENERGY
ZEROTH LAW – If two bodies are 1 2
KE= m v , 2 2
1 J =1 kg∗m /s ,
individually in equilibrium with a 2
separate third body, then the first 1 J =1 N∗m=1kg∗m / s
2 2

two bodies are also in thermal

equilibrium with each other. ENERGY CONVERSION FACTORS
FIRST LAW - Also known as the 1 calorie (cal) = 4.184 joules (J) (exact)
1 Calorie (Cal) = 1000 calories (cal)
law of conservation of energy, states
1 kilowatt-hour (kWh) = 3.60 ×106 joules( J )
that energy can neither be created
nor destroyed, but it can be changed
from one form to another. THERMODYNAMIC SYSTEM
A thermodynamic system is a body of matter and/or radiation
SECOND LAW - The entropy in an separate from its surroundings that can be studied using the laws
isolated system always increases. of thermodynamics. A thermodynamic system may be an open
Any isolated system spontaneously system, a closed system, or an isolated system. (Note: everything
evolves towards thermal equilibrium else is considered as the surroundings)
which is the state of maximum
entropy of the system.  Open system – Can interact with its surroundings by
THIRD LAW - The entropy of a exchanging both matter and energy.
system approaches a constant value  Closed system – May exchange heat, experience forces, and
as the temperature approaches exert forces, but does not exchange matter.
absolute zero.  Isolated system – Does not exchange matter or energy with
its surroundings.

SOME FORMS OF ENERGY ENERGY FLOW AND CONSERVATION OF ENERGY

Electrical – Heat or Thermal Energy Conservation of Energy requires that the total energy change in the
– Light or Radiant Energy – Nuclear system and the surroundings must be zero.
– Chemical
∆ Energy universe =0=∆ Energy system + ∆ Energy surroundings
 NATURE OF ENERGY
THERMOCHEMIS
INTERNAL ENERGY
TRY  The total amount of kinetic and potential energy a system
STATE FUNCTION: possesses.
IT IS A MATHEMATICAL FUNCTION  The change in the internal energy of a system only depends
WHOSE RESULT ONLY DEPENDS ON THE on the amount of energy in the system at the beginning
INITIAL AND FINAL CONDITIONS, NOT and end.
ON THE PROCESS USED
∆ Energy=∆ Energy final−∆ Energyinitial
NOTE: THE CHANGE IN ALTITUDE DEPENDS ∆ Energy reaction =∆ Energy product −∆ Energy reactants
ONLY ON THE DIFFERENCE BETWEEN
INITIAL AND FINAL VALUES, NOT ON THE
PATH TAKEN. ENERGY DIAGRAMS
 A “graphical” way of showing the direction of energy flow
during a process. It shows the amount of relative potential
energy in each step of a reaction.
THERMAL EQUILIBRIUM  If the final condition has a larger amount of internal energy
A state in which two or more objects
than the initial condition, the change in the internal energy
or systems have the same
will be (+).
temperature and there is no net flow
 If the final condition has a smaller amount of internal
of heat between them. This means
energy than the initial condition, the change in the energy
that the rate of heat transfer between
will be ( - ).
the objects is equal, and there is no
change in the overall temperature of
the system.
Temperature – a measure of the
thermal energy (total kinetic energy
of the particles of an object) ENERGY FLOW
 When energy flows out of a system, it must all flow into the
Heat – the transfer of thermal surroundings.
energy between two bodies that are  When energy flows out of a system, ∆ E system is ¿.
at different temperatures.  When energy flows into the surroundings,∆ E surroundings is ¿.
 Therefore;
−∆ Energy system =∆ Energy surroundings
ENERGY EXHANGE
Energy is exchanged between the ∆ Energy system <0 ( negative )
system and surroundings through ∆ Energy surroundings >0( positive)
heat and work.  When energy flows into a system, it must all come from the
surroundings.
q=¿ heat (thermal) energy
 When energy flows into a system, ∆ E system is ¿.
w=¿ work energy  When energy flows out of the surroundings,∆ E surroundings is ¿.
q and w are NOT state functions,  Therefore;
their value depends on the process. ∆ Energy system =−∆ Energy surroundings
∆ E=q +w ∆ Energy system >0 ( positive )
∆ Energy surroundings <0(negative)
 HEAT AND WORK
THERMOCHEMIS
HEAT EXCHANGE
TRY  The exchange of thermal energy between the system and
HEAT AND WORK ARE TWO DIFFERENT surroundings.
WAYS OF TRANSFERRING ENERGY  Occurs when system and surroundings have difference in
FROM ONE SYSTEM TO ANOTHER. temperature.
 Heat flows from matter with high temperature to matter
IN THERMODYNAMICS, HEAT AND with low temperature until both objects reach the same
WORK ARE BOTH WAYS IN WHICH temperature.
ENERGY CAN BE TRANSFERRED TO OR
FROM A SYSTEM. THE FIRST LAW OF
QUANTITY OF HEAT ENERGY ABSORBED HEAT CAPACITY
THERMODYNAMICS STATES THAT THE
CHANGE IN INTERNAL ENERGY OF A
 When a system absorbs heat, its temperature increases.
SYSTEM IS EQUAL TO THE HEAT ADDED  Increase in temperature is directly proportional to the
TO THE SYSTEM MINUS THE WORK amount of heat absorbed
DONE BY THE SYSTEM.  The proportionality constant is called heat capacity, C.
(Note: units of C are J/°C or J/K)
q=C x ∆ T
 The heat capacity of an object depends on its mass/on the
RELATION BETWEEN HEAT type of material.
AND WORK
SPECIFIC HEAT CAPACITY
HEAT – the transfer of thermal  Heat capacity is a property that describes how much energy
energy between two bodies that are is needed to change the temperature of a material. Objects
at different temperatures and is not with a high specific heat capacity require a greater change
equal to thermal energy. in energy to change their temperature and vice versa for
objects with a low specific heat capacity.
WORK – the force used to transfer  The specific heat capacity is the amount of heat energy
energy between a system and its required to raise the temperature of one gram of a substance
surroundings and is needed to create 1°C.
heat and the transfer of thermal  the molar heat capacity is the amount of heat energy
energy. required to raise the temperature of one mole of a substance
Example; Both can cause a 1°C.
temperature increase. Heat transfers
energy into a system, such as when QUANTIFYING HEAT ENERGY
the sun warms the air in a bicycle  The amount of heat gained or lost by a sample ( q ) can be
tire and increases the air's calculated using the equation q=mcΔT , where m is the mass
temperature. Similarly, work can be of the sample, c is the specific heat, and ΔT is the
done on the system, as when the temperature change.
bicyclist pumps air into the tire.
THERMOCHEMIS PRESSURE – VOLUME WORK
EXCHANGING ENERGY BETWEEN SYSTEMS AND
TRY SURROUNDINGS
PRESSURE WORK IS WORK THAT IS THE  Exchange of heat energy:
RESULT OF A VOLUME CHANGE Q = mass × specific heat × ∆ T
AGAINST EXTERNAL PRESSURE.  Exchange of work:
(WORK DONE BY A GAS) w=−¿ Pressure × ∆ Volume
GASES CAN DO WORK THROUGH
EXPANSION OR COMPRESSION AGAINST MEASURING ∆ E, CALORIMETRY AT CONSTANT VOLUME
CONSTANT EXTERNAL PRESSURE. WORK Since ∆ E=q +w , we can determine ∆ E by measuring

DONE BY GASES IS ALSO SOMETIMES q and w .
CALLED PRESSURE-VOLUME.
 In practice, it is easiest to do a process in such a way that
AS LONG AS THE EXTERNAL PRESSURE IS there is no change in volume, w=0
KEPT CONSTANT; (Note: at constant volume, ∆ E system =q system)
−Work =External Pressure∗Change∈Volume
 The surroundings is called a bomb calorimeter and is usually
w=−P ∆ V made of a sealed, insulated container filled with water.
q surroundings=qcalorimeter =−q system
−∆ E reaction =q cal=C cal × ∆ T

BOMB CALORIMETER
 Used to measure ∆ E because it is a constant volume system.
 In practice, it is easiest to do a process in such a way that
there is no change in volume, w=0

PRESSURE – VOLUME WORK

To convert the units to Joules use
ENTHALPY
 The enthalpy, H, of a system is the sum
101.3 J = 1 atm*L
of the internal energy of the system and
the product of pressure and volume.
H=E + PV
 The enthalpy change, ∆ H , of a reaction is
The heat evolved in a reaction at a constant pressure.
∆ H reaction =qreaction at constant pressure
 Usually ∆ H and ∆ E are similar in value, the difference is
largest for reactions that produce or use large quantities of
gas.
 ENDOTHERMIC AND EXOTHERMIC
THERMOCHEMIS
REACTIONS
TRY
MOLECULAR VIEW OF EXOTHERMIC REACTIONS
ENTHALPY, NORMALLY DENOTED H , IS  It is when the temperature rises due to release of thermal
A THERMODYNAMIC PROPERTY; IT IS energy.
EQUAL TO THE SUM OF INTERNAL  Extra thermal energy comes from the conversion of some of
ENERGY PLUS THE PRODUCT OF THE
the chemical potential energy in the reactants into kinetic
PRESSURE AND THE VOLUME, I.E.
energy in the form of heat.
H=U + pV .
 Old bonds are broken, and new bonds are made.
 Products of the reaction have less chemical potential energy
CHANGES IN ENTHALPY DURING HEATING
AND COOLING OPERATIONS ARE
than the reactants.
IMPORTANT; THE CHANGE IN ENTHALPY ∆H  Energy is released as heat
IS GIVEN BY. Δ H =Δ U + Δ PV .
MOLECULAR VIEW OF ENDOTHERMIC REACTIONS
 The temperature drops due to absorption of thermal energy.
 Required thermal energy comes from the surroundings.
MEASURING ∆H
 Old bonds are broken, and new bonds are made.
CALORIMETRY AT CONSTANT  Products of the reaction have more chemical potential
PRESSURE energy than the reactants
 To acquire extra energy, some of the thermal energy of the
Reactions done in aqueous are at surroundings is converted into chemical potential energy
constant pressure stored in the products.

Open to the atmosphere ENTHALPY OF REACTIONS

Calorimeter is often nested foam  The enthalpy change in a chemical reaction is an extensive
cups containing the solution: property (Note: The more reactants you use, the larger the
enthalpy change.)
q reaction=−q solution
 The Heat of Reaction is the change in the enthalpy of a
¿−(mass solution∗C s ,solution∗∆ T ) chemical reaction that occurs at a constant pressure.
 We calculate the enthalpy change for the number of moles of
 ∆ H reaction =qconstant pressure
reactants in the reactions as written;
¿ q reaction C 3 H g ( g )+5 O2 ( g ) → 3 CO2 ( g ) +4 H 2 O ( g ) ∆ H=−2044 kJ
To get ∆ H reaction per mol, divide by −2044 kJ 1 mol C3 H 8
∆ H reaction for 1 mol C 3 H 8 −2044 kJ ∨
the number of moles. 1 mol C 3 H 8 −2044 kJ
∆ H reaction for 5 mol O2=−2044 kJ
−2044 kJ 5 mol O2
∨
5 mol O2 −2044 kJ
THERMOCHEMIS MEASURING ∆ H CALORIMETRY AT
CONSTANT PRESSURE
TRY RELATIONSHIPS INVOLVING ∆H_RXN
HESS’S LAW
 When reactions is multiplied by a factor, ∆ H rxn is multiplied
THE CHANGE IN ENTHALPY FOR A by a factor since ∆ H rxn is extensive.
STEPWISE PROCESS IN THE SUM OF
ENTHALPY CHANGES OF THE STEPS.
C ( s )+O2 ( g ) →C O2 ( g ) ∆ H=−393.5 kJ
2C ( s )+2 O2 ( g ) → 2C O2 ( g ) ∆ H =2 (−393.5 kJ )
THE LAW STATES THAT THE CHANGE IN ¿ 787.0 kJ
ENTHALPY FOR A REACTION IS THE SAME
WHETHER THE REACTION TAKES PLACE IN
ONE OR A SERIES OF STEPS. THE HESS'S  If a reaction is reversed, then the sign of ∆H is reversed;
LAW CAN ALSO BE STATED AS THE C O2 ( g ) → C ( s )+O2 ( g ) ∆ H=+393.5 kJ
ENTHALPY CHANGE FOR A CHEMICAL
REACTION IS THE SAME REGARDLESS OF
THE PATH BY WHICH THE REACTION RELATIONSHIPS INVOLVING ∆H_RXN HESS’S LAW
OCCURS.
 If a reaction can be expressed as a series of steps, then the
∆ H rxn for the overall reaction is the sum of the ehats of
reaction for each step.

[ 2 N O 2 ( g ) →2 NO ( g ) +O2 ( g ) ] ∆ H °=+173 kJ
1
2
[ 2 N 2 ( g ) →5 O2 ( g ) +2 H 2 O ( l ) ] → 2 HN O3 ( aq ) ¿ ∆ H °=+255 kJ

3 [ N 2 ( g )+ O2 ( g ) →6 NO ( g ) ] ∆ H °=−181 kJ

3 N O2 ( g ) + H 2 O ( l ) →2 HN O3 ( aq )+ NO(g)∆ H °=−49 kJ
 STANDARD CONDITIONS
THERMOCHEMIS
STANDARD STATE – STATE OF A MATERIAL AT A DEFINED
TRY SET OF CONDITIONS
ALL VALUES HAVE UNITS OF KJ/MOL  Pure gas at exactly 1 atm pressure
AND PHYSICAL CONDITIONS OF 298.15  Pure solid or liquid in its most stable form at exactly 1 atm
K AND 1 ATM, REFERRED TO AS THE pressure and temperature of interest (usually 25°C)
"STANDARD STATE."  Substance in a solution with concentration 1 M

THESE ARE THE CONDITIONS UNDER

WHICH VALUES OF STANDARD ENTHALPIES
STANDARD ENTHALPY CHANGE, ∆ H °
OF FORMATION ARE TYPICALLY GIVEN.  When all reactants and products are in their standard states.
 The term "enthalpy change" only applies to reactions done at
constant pressure. That is how most lab reactions are done -
in tubes or flasks (or whatever) open to the atmosphere, so
that the pressure is constant at atmospheric pressure.
SELECTED STANDARD HEATS  Everything has to be present in its standard state. That is the
OF FORMATION AT 25°C physical and chemical state that you would expect to find it in
(298K) under standard conditions.

STANDARD ENTHALPY FORMATION, ∆ H °

 The standard enthalpy of formation of a substance is the
enthalpy change that occurs when 1 mole of the substance is
formed from its constituent elements in their standard
states.
 A pure element in its standard state has a standard enthalpy
of formation of zero.

FORMATION REACTIONS
Chemical reactions that form 1 mole of a substance from its
constituent elements in their standard states.

 Standard state of an element; (Appendix) ∆ H f °=0

 Since 1 mole of compound is required, therefore the
coefficients of the reactants may be fractions.
∆ H ° reaction =∑ n ∆ H ° f ( products )−∑ n ∆ H ° f ( reactants )