THERMODYNAMICS

CHEM 18
THERMOCHEMISTRY
• This is a branch of chemistry that is concerned with the effects of heat
accompanying various chemical reactions.
SYSTEM
• This is the part of the universe that thermochemistry concerns itself
with.
SURROUNDINGS
• This is what is referred to as everything outside of a system.

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TYPES OF SYSTEM
OPEN SYSTEM
• This is a system that is capable of experiencing external interaction.
CLOSED SYSTEM
• This is a system wherein the substances within the system experience no
external interaction but energy is free to be transferred.
ISOLATED SYSTEM
• This is a system wherein neither matter nor energy is able to experience
external interaction.

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ENERGY
• This is a quantitative property transferred from one object to another in
order to perform WORK.
KINETIC ENERGY
• This is the energy observed from a moving object.
POTENTIAL ENERGY
• This is the energy associated with attraction and repulsion between
objects. It takes into consideration condition, position, and composition.

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HEAT AND WORK
• This is the energy transferred between a system and the surroundings.
QUANTITY OF HEAT (q)
• This is the amount of heat required to change the temperature of a
certain substance.
WORK
• This is the energy transfer that happens when an object is moved by an
external force to a certain distance.

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INTERNAL ENERGY (U)
• Any energy entering the system carries a positive sign.
• If heat is absorbed by the system, q is POSITIVE.
• If work is done on the system, w is POSITIVE.

• Any energy leaving the system carries a negative sign.

• If heat is given off by the system, q is NEGATIVE.
• If work is done by the system, w is NEGATIVE.

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THERMOCHEMICAL PROCESSES
EXOTHERMIC PROCESS
• This process increases the temperature in an isolated system.
• This also causes heat to be given off in a non-isolated system.

ENDOTHERMIC PROCESS
• This process decreases the temperature in an isolated system.
• This also causes heat to be absorbed in a non-isolated system.

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ENTHALPY (H)
• This refers to the sum of the internal energy of the system and its
pressure-volume product.
• Similarly, the enthalpy change is the sum of the change in internal energy
and changes in pressure and volume.

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PROPERTIES OF ENTHALPY (H)
• The value of ΔH depends on the quantity of material. It is an extensive
property.
• ΔH depends on the physical state of each component of the system.
Essential to include the state of all reactants and products.
• The magnitude of ΔH is the same for the reverse process but opposite
in sign.

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HESS’S LAW
• The total enthalpy change during a complete reaction will be the same
whether it is made in one step or several other steps. Regardless, the
sum of all the changes will account for the total enthalpy change.
• If a reaction is reversed, the sign of ΔH is also reversed.
• The magnitude of ΔH is directly proportional to the quantities of
reactants and products.
• If the coefficients in a balanced equation are multiplied by an integer, the
value of ΔH is multiplied by the same integer.

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STANDARD ENTHALPY CHANGE
• This refers to the heat transferred in the reaction with reactants and
products in their standard states (25 °C, 1 atm).
• The ΔH that accompanies the formation of one mole of the compound
from its elements with all substances in their standard states at 25 ° C.

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SPONTANEOUS REACTIONS
• This is a process that occurs without external intervention.
• It is driven by a tendency to reach a state of minimum potential energy.
• This reaction may be fast or slow.
• If a process is spontaneous then the reverse of it will be non-
spontaneous.
• Both spontaneous and non-spontaneous processes are possible, but only
spontaneous processes will occur without intervention. Non-
spontaneous processes require an outside force.

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SPONTANEITY and ENTROPY
SPONTANEITY
• This is associated with a decrease in the energy of the system.
• Generally, -ΔH will be regarded as spontaneous.
ENTROPY
• This is a measure of randomness.
• This usually increases when a pure solid or liquid dissolves in a solvent.
2ND LAW OF THERMODYNAMICS
• All spontaneous processes produce an increase in the entropy of the
universe.

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GIBBS FREE ENERGY
• This is another criterion for judging spontaneity.
• It makes use of both enthalpy and entropy in a single value.
• If ΔG is (-), the reaction is spontaneous.
• If ΔG is (+), the reaction is nonspontaneous.
• If ΔG is (0), the reaction is at equilibrium.

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GIBBS FREE ENERGY
• For exothermic reactions and reactions that lead to a more disordered
state, ∆G is negative at all temperatures and the reaction is spontaneous
at all temperatures.
• For exothermic reactions and reactions that lead to a less disordered
state, the reaction is spontaneous at low temperatures.
• For endothermic reactions and reactions that lead to a less disordered
state, ∆G is positive at all temperatures and the reaction is
nonspontaneous at all temperatures.
• For endothermic reactions and reactions that lead to a more disordered
state, the reaction is spontaneous at high temperatures.

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