Thermochemistry

● The study of energy changes that occur during chemical reactions and changes of
state (exo vs. endo thermic)
● Energy is the ability to do work or produce heat.
● Heat is a form of energy and energy is measured by force exerted over a distance
(F*D)
● Potential energy is energy due to composition or position of an object, such as
energy in chemical bonds
● Kinetic energy is energy in motion
● Law of conservation of energy: energy can be converted between forms but
cannot be created or destroyed
● Energy in= energy out
● Energy stored in a substance because of its position is chemical potential energy,
stored energy in the chemical bond
● q= symbol for heat
○ Heat is energy in the process of flowing from a warmer to a cooler place
○ If a warmer object loses heat, its temp goes down
○ If a cooler object gains heat, its temp goes up
● A calorie is the amount of heat energy needed to raise the temp one gram of pure
water by 1°C in the metric system
● Kilocalorie=1,000
● I calorie= 1g*1°C
● The SI unit of energy is the Joule. One Joule is 0.2390 calories.
● A nutritional calorie is a kilocalorie
● Specific heat is the amount of heat energy needed to raise the temperature of 1g
of a substance 1°C.
● Water has a high specific heat, at 4.18 J/g*K
● It’s represented by “c”
● As a result of different substances having different compositions, each substance
has its own specific heat
 ● Specific heat is a physical property
● Different materials heat up at different rates
● q=c*m*deltaT
● Heat= specific heat capacity* mass*change in temperature
Measuring Heat
● Heat changes occur during chemical and physical processes that are measured
accurately and precisely using a calorimeter.
● A calorimeter is an insulated device used for measuring the amount of heat
absorbed or released during a chemical or physical process.
● Enthalpy (H)= heat content of a system at constant pressure
○ Cannot measure the exact energy or enthalpy of a substance.
○ Can measure changing in enthalpy, or the heat that was absorbed or
released in chemical reaction
○ DeltaH= change in enthalpy of a reaction/enthalpiy(heat) of reaction
○ In exothermic reactions, delta H is negative, while in endothermic reactions,
delta H is positive.
○ Reactions- products= enthalpy of a reaction (final-initial enthalpy
● A thermal chemical reaction is a balanced chemical equation that states all
reactants and products and the energy change.
● The enthalpy/heat of combustion of a substance is the enthalpy change for the
complete burning of one mole of the substance.
● Standard enthalpy changes have the symbol delta H°
○ Standard or room temperature/25°C and 298°K
○ Table I is the amount of heat gained or lost during a reaction.
○ Greater than negative delta H, the more stable the product of the reaction
will be. This is because more envy will be needed to reverse the reaction and
decompose the compound into its elements.
○ The energy released in the formation of a compound is identical to the
amount of energy required to decompose the compound into its elements.
○ More stable compounds have a smaller delta H, whether it’s negative or
positive
Heating and Cooling Curves
 ● Heat needed to melt something= heat of fusion
● Going up is a hearing curve, while going down is a cooling curve.
● Level lines indicate temperature constants, which are phase changes, meaning
either boiling and condensation or freezing and melting
● At the end of the solid line, the solid begins to melt, and by the end it is all liquid.
● At the end of the liquid line, the liquid begins to boil, and by the end it is all gas.
● Flat lines indicate a mixture of phases, or equilibrium.
● Reason, crystallization, and fusion are all the same thing
● Coming out of a hot shower and being splash of water both make you feel cool.
● Added heat energy causes a temperature change or a phase change.
● Heat of fusion is the specific heat allowed for phase change from a solid to a liquid
● Heat of vaporization is the specific heat for a phase change from a liquid to a gas.
Energy Changes and Changes of State
● A substance needs heat to evaporate or vaporize.
● Liquid to gas— vaporization
○ DeltaHvap
○ Enthalpy equals heat of vaporization
○ Endothermic
○ DeltaHvap of water is 2260 J/g
○ Melting is endothermic, freezing is exothermic
○ Boiling is endothermic, condensation is exothermic
○ Phase change: KE stays the same, potential energy increases
● Solid to liquid= melting
○ DeltaHfus
○ Enthalpy of fusion
○ Heat required to melt 1 g of solid
○ Endothermic
○ DeltaHfus of water is 334 J/g
 ● Heat of fusion: change a unit of mass of a substance from a solid to a liquid at its
melting point
Entropy
● Exothermic reactions are spontaneous, they happen often because they don’t
require heat
● Entropy is the measure of disorder of a system, measure of randomness of a
system. Symbol=s
● The law of disorder is the second law of thermodynamics, spontaneous processes
always proceed in such a way that the entropy of the universe increases.
● The law of this order states of things move spontaneously in the direction of
maximum chaos and lower energy/enthalpy.
○ Exothermic reactions go in this direction
○ Delta S is positive, delta H is negative
● Changes of state: entropy increases on a solid changes within a liquid changes to a
gas because these changes of state result in freer movement of the particles.
● When gas dissolved in a liquid or solid solvent, motion of the particles are limited
and entropy of the gas decreases.
● When the number of gas particles increases, the entropy of the system usually
increases because more random arrangements are possible.
● Dissolving a solid/ liquid to form solution: when solute particles are dispersed in a
solvent, the disorder of the particles and entropy of the system increases.
● Temperature increase causes an increase in disorder, increase in KE, and increase
in entropy.
● Cooling something= exothermic, heating=endothermic
● Sign in front of Delta H indicates exo or endothermic
● Divide the number of joules by 1000 to get the number kilojoules
● Spontaneous reactions occur naturally under states conditions of temperature,
gases, pressure, etc.
● Non-spontaneous reactions don’t occur under stated conditions
● The two tendencies of govern every system or energy and randomness/enthalpy
and entropy
● A decrease in enthalpy and an increase in entropy are the favorable outcomes. This
means exothermic and more random reactions
● Major compromises between the tendency to lower energy and the tendency to
increase the disorder state.
● Size and direction of heat changes and entropy changes determine whether a
reaction is spontaneous.
● Gibb’s Free Energy Change/ Gibb’s Equation
○ Delta G= free energy
 ○
○ Enables us to predict whether he actually be spontaneous under the given
conditions
○ If delta G is negative, the reaction is spontaneous.
○ If delta G is positive, the reaction is nonspontaneous.
○ The temperature is always in Kelvin, there is never a negative temperature.
○ Changes in temperature are a factor
○ The temperature rises, the disorder factor becomes more important.

○
Chemical Kinetics: The study of reaction rates and the factors that determine them
● Reaction rate is expressed in molarity/sec.
● Brackets around the formula for substance denote the molar concentration.
● The collision theory states that atoms, ions, and molecules must collide with each
other in order to react
● Collide faster means rate of reaction is faster.
● Following 3 statements explain the collision theory
 ○ Particles must collide order to react
○ The particles must collide with correct orientation
○ The particles must collide with enough energy to to form an unstable
activated complex, also called the transition state, which is an intermediate
particle(s).
● To get to the activated complex (minimum energy) activation energy of the
reaction (AE or Ea)
● Particles that collide with less than the activation energy don’t form a reaction.
● Always have to add energy
● Reaction, overcome that division energy barrier for an activated complex, then
release energy inform product at a lower energy level.
● The difference between the starting and energy an ending energy is the heat of
reaction
● Catalysts lower the activation energy help get to the activated complex.
● An inhibitor slows down the action of a catalyst, slowing reaction rates and
increasing activation energy.
● Always have to add energy
● In an exothermic reaction, molecules collide with enough energy to overcome the
activation energy barrier, form an activated complex, and the release products and
form products at a lower energy level.
● The difference between the starting and ending energy is the heat of reaction
● Catalysts lower/ change the activation energy to get to the activation energy
sooner.
● An inhibitor slows down the action of a catalyst, slowing reaction rates
(changing/increasing activation energy)
Chemical Equilibrium: A State of Dynamic Balance
● The rates of the foreword and reverse reactions are constant and equal, they don’t
change
● Equilibrium is a dynamic condition where the rates of opposing processes are
equal.
● Types of equilibrium:
○ Phase equilibrium: 2 phases exist at the same temperature
○ Solution equilibrium: state of dissolving equals state of crystallization
○ Chemical equilibrium:
● Chemical equilibrium: AState if Dynamic Balance
○ Reversible reaction
○ Rate of forward reaction equals the rate if the reverse reaction
○ Concentration of reactants and products are constant but not necessarily
equal.
○ [reactants] and [products] are equal (molar concentration)
○ MOST chemical reactions are reversible, and the concept of equilibrium
requires a reversible reaction
○ German scientist Fritz Haber won a Nobel in 1918 for the Haber process, or
the synthesis of ammonia from its elements
■ N2+3H. <=>2NH3
○ Reversible reactions are ones that can be performed in both forward and
reverse reactions
○ As a system approaches equilibrium, both the foreword and reverse
reactions are occurring
○ Concentrations of the reactions decrease at first, while the concentration of
the product decreases
○ Before all the reactants are used up, the products become constant.
○ Rates of opposing reactions are equal
○ The law of chemical equilibrium states that, at a given temperature, a
chemical system may reach a state at which a particular ratio of reactant
and product concentrations have a constant value.
■ aA+bB<=>cC+dD
■ The lowercase letters are molar concentration ratios/coefficients
■ Uppercase letters are reactants and products
○ Mass action expression: a fraction formed from the concentration of the
reactants and products, with each concentration raised to the power of its
coefficients. At a particular temperature, the mass action expression for a
reversible reaction will be constant.
■ Products/reactants
■ Right side/left side
■ [C]c[D]d/[A]a[B]b
■ Ratio: equilibrium constant expression (Keq)
■ If the Keq is a large number, there are more products than reactants
at equilibrium
■ If the Keq is a small number, there are more reactants than products
at equilibrium
■ Eliminate solids from chemical equilibrium expression
■ KSP indicates more soluble (solubility product constant) tells you
how much will dissolve once it reaches equilibrium.
○ Le Châtlier’s Principle
■ Effects of stress on a system at equilibrium
■ If a stress is applied to a system at equilibrium, the system them
shifts in the direction that relieves the stress and reestablishes the
equilibrium.
■ If there is a change in concentration, the system will shift to use up
the excess.
● To favor the forward reaction, the system shifts to the right
● Ex: A+B<=>C+D
○ If more A is added, the forward reaction will increase to
use up the extra A.
 ○ This increases the probability of it reacting with B to
produce more C and D.
○ The concentration of B will then decrease because it is
reaction more with A.
● Common ion effect (concentration increase)
○ 2AgCl<=>2Ag+Cl2
○ Adding NaCl increases the concentration of Cl, a
common ion.
○ This will end up favoring the left/ a reverse reaction
because chloride ions increase and silver ions decrease.
■ The shifts after a temperature change depend on whether a reaction
is exothermic or endothermic
● An increase in temperature favors the endothermic reactions
● A decrease in temperature favors the exothermic reactions
■ Change in pressure (gases only)
● The coefficients of a balanced equation give a molar ratio
● For gases, the coefficients also give a volumetric ratio
● An increase in pressure favors the side with less moles, while
an increase in pressure favors the side with more moles.
● If the volumetric ratios are equal, a change in pressure has no
effect.
■ Adding a catalyst
● Favors neither reaction
● Increases both rates equally