First Law of Thermodynamics - Full Reviewer

I. Introduction to Thermodynamics
 Definition: Thermodynamics is the branch of science concerned with the relationships
between heat, work, temperature, and energy.
 Key Concept: It studies the conversion of thermal energy into other forms of energy
and vice versa.
II. Fundamental Concepts
1. Thermal Energy: Energy generated by the motion of particles within a substance.
2. Internal Energy (U): The total kinetic and potential energy of all particles in a system.
o It is a state function, meaning it depends only on the state of the system, not
the process used to reach that state.
o The change in internal energy (ΔU\Delta U) can be measured, but not the
absolute internal energy itself.
III. First Law of Thermodynamics
 Also known as the Law of Conservation of Energy.
 Statement: Energy cannot be created or destroyed, only transformed from one form to
another.
 Mathematical Expression:
where:
o ΔU = change in internal energy

o q = heat absorbed (+) or released (-) by the system

o w = work done on the system (+) or by the system (-)

IV. Heat and Work in Thermodynamics

1. Heat (q)
o Positive (+q): Heat is absorbed by the system (endothermic process).

o Negative (-q): Heat is released by the system (exothermic process).

2. Work (w)
o Positive (+w): Work is done on the system (compression).

o Negative (-w): Work is done by the system on the surroundings (expansion).

V. Applications of the First Law of Thermodynamics

1. Heating Water in a Pot
o As heat is added, internal energy increases.

o The water evaporates, doing work on the surroundings.

2. Burning Fuel in an Engine

o Chemical energy in fuel converts to heat.

o The heat expands gases, doing work on the piston.

3. Piston-Cylinder Systems
 o If a gas expands inside a piston, it does work (-w), decreasing ΔU.

o If compressed, work is done on the gas (+w), increasing ΔU.

VI. Sample Calculations

1. Example 1: A system absorbs 50 J of heat and does 15 J of work on the surroundings.
Determine ΔU.

o Since ΔU is positive, the internal energy of the system increases.

2. Example 2: A system absorbs 50 J of heat but performs 65 J of work on the

surroundings.
o

Since ΔU is negative, the internal energy decreases.

3. Example 3: A gas expands from 2.5 L to 8.5 L against an external pressure of 1.5 atm,
releasing 400 J of heat. Work is calculated using:

o The negative ΔU means the system lost energy.

VII. Key Takeaways

 The first law of thermodynamics states that energy is conserved.
 Heat and work affect the internal energy of a system.
 Signs matter: Energy absorbed is positive, energy lost is negative.
 Application in real-life: Engines, refrigerators, biological systems, and power plants
all follow thermodynamic principles.

Enthalpy: Definition and Importance

 Enthalpy (H) is a thermodynamic property representing the total heat content of a
system at constant pressure.
 It is a state function, meaning that its change (ΔH) depends only on the initial and
final states, not on the path taken.
 The change in enthalpy is given by:
 Key Importance: Enthalpy changes help us understand the energy flow in chemical
reactions.
Types of Enthalpy Changes
1. Exothermic Reactions (ΔH < 0, negative)
o Heat is released to the surroundings.

o The system loses energy.

o Example: Combustion of fuels (burning wood)

2. Endothermic Reactions (ΔH > 0, positive)

o Heat is absorbed from the surroundings.

o The system gains energy.

o Example: Photosynthesis

Measuring Enthalpy Change

 Enthalpy change (ΔH) is measured using a calorimeter at constant pressure.
o Formula for heat calculation:

o q = heat absorbed or released

o m = mass of the substance

o c = specific heat capacity

o ΔT = change in temperature

Standard Enthalpy Changes

 Standard Enthalpy Change of Reaction (ΔH° or ΔH_rxn°):
o The enthalpy changes under standard conditions (298K and 1 atm).

o Calculated using Hess’s Law and standard enthalpy of formation values.

 Standard Enthalpy of Formation (ΔH_f°):

o The enthalpy changes when one mole of a compound is formed from its
elements in their standard states.
o Equation:

Sample Calculations
1. Calculate the standard enthalpy change for the reaction:

Given:
o ΔH_f° [NH₃(g)] = -46 kJ/mol

o ΔH_f° [N₂(g)] = 0 kJ/mol

o ΔH_f° [H₂(g)] = 0 kJ/mol

Solution:
Answer: -92 kJ/mol (Exothermic reaction)
2. Calculate the enthalpy change for the reaction:

o ΔH_f° [HCl(g)] = -92.3 kJ/mol

o ΔH_f° [F₂(g)] = 0 kJ/mol

o ΔH_f° [HF(g)] = -271.1 kJ/mol

o ΔH_f° [Cl₂(g)] = 0 kJ/mol

Solution:

Answer: -357.6 kJ/mol (Exothermic reaction)

Hess’s Law
 Definition: The total enthalpy change for a reaction is independent of the path
taken. It is the sum of the enthalpy changes of individual steps.
 Application: If a reaction can be expressed as the sum of multiple steps, the enthalpy
change for the overall reaction is the sum of the enthalpy changes for those steps.

Short Quiz
True or False
1. A positive enthalpy change indicates an exothermic reaction. (False)
2. Standard enthalpies of formation are always positive values. (False)
3. The internal energy of a system is the sum of all kinetic and potential energies of a
system. (True)
4. If a system absorbs heat and does work, its internal energy will always increase.
(False)
5. The change in internal energy (ΔU) of a system depends only on the initial and
final states, not the path taken. (True)

Key Takeaways
 Exothermic reactions release heat (ΔH < 0), while endothermic reactions
absorb heat (ΔH > 0).
 Calorimetry is used to measure heat transfer, utilizing the formula q = mcΔT.
 Standard enthalpy of formation values (ΔH_f°) help in calculating enthalpy
changes in reactions.
  Hess’s Law simplifies complex reactions by breaking them into steps.

CHEMICAL THERMODYNAMICS: SPONTANEITY AND ENTROPY REVIEWER

1. Spontaneity of a Process
A spontaneous process occurs without continuous external intervention and moves a
system to a lower, more thermodynamically stable energy state. A nonspontaneous
process requires continuous input of energy to occur.
 Examples:
o Water evaporating is spontaneous under normal conditions.

o The electrolysis of water into hydrogen and oxygen is nonspontaneous and

requires energy.
The spontaneity of a process depends on entropy (ΔS) and free energy change (ΔG).

2. Entropy (S) – Measure of Disorder

Entropy is a state function that measures randomness or disorder in a system.
 Higher entropy = Greater disorder
 Lower entropy = More ordered system
Entropy Change (ΔS):

 Positive ΔS → Increase in disorder (e.g., solid to liquid or gas)

 Negative ΔS → Decrease in disorder (e.g., gas to liquid or solid)
Examples of Entropy Change Predictions:
 Increase in entropy:
o 2KClO₃ (s) → 2KCl (s) + 3O₂ (g) (gas is formed)

o CaCO₃ (s) → CaO (s) + CO₂ (g)

 Decrease in entropy:
o 2H₂ (g) + O₂ (g) → 2H₂O (g) (fewer gas molecules)

o C (s, graphite) → C (s, diamond) (more ordered solid structure)

Entropy & Temperature:

 At higher temperatures, kinetic energy increases, and entropy also increases.

3. The Second Law of Thermodynamics

“All natural processes occur in the direction that increases the entropy of the universe.”

 A process is spontaneous only if the total entropy of the universe increases.

 Exothermic and endothermic reactions can be spontaneous if the entropy of the
universe increases.
4. The Third Law of Thermodynamics
“The entropy of a perfect crystal at absolute zero (0 K) is exactly zero.”
 At absolute zero, molecular motion ceases, leading to zero disorder.

5. Entropy Change in Reactions

Example Calculation:
For the reaction C (s) + CO₂ (g) → 2CO (g)
 C (s): 5.740 J/mol K
 CO₂ (g): 213.74 J/mol K
 CO (g): 197.67 J/mol K

Since ΔS° is positive, entropy increases in this reaction.

6. Gibbs Free Energy (G) – Criterion for Spontaneity

 ΔG < 0 → Spontaneous process

 ΔG > 0 → Nonspontaneous process
 ΔG = 0 → System at equilibrium
 Effect of Temperature on Spontaneity:

ΔH ΔS High T Low T

+ (disorder
- (exo) Spontaneous Spontaneous
↑)

Nonspontaneo
- (exo) - (order ↑) Spontaneous
us

+ + (disorder Nonspontaneo
Spontaneous
(endo) ↑) us

+ Nonspontaneo Nonspontaneo
- (order ↑)
(endo) us us
Example Calculation:
For a reaction where:
 ΔH = -50 kJ/mol
 ΔS = +100 J/mol K
 T = 298 K

Since ΔG is negative, the reaction is spontaneous.

7. Temperature Dependence of Spontaneity

A process may be spontaneous at one temperature but nonspontaneous at another.
Example:
 CO (g) + H₂O (g) → CO₂ (g) + H₂ (g)
o ΔG = -28.6 kJ at 298 K (Spontaneous)

o ΔG = +42.67 kJ at 2000 K (Nonspontaneous)

This shows that temperature affects spontaneity depending on ΔH and ΔS values.

8. Application to Melting and Freezing

Melting of Ice:
 H₂O (s) → H₂O (l) (ΔS = 22.1 J/K, q_surr = -6.00 kJ)
At -10°C (263 K):

 ΔS is negative → Nonspontaneous
At 10°C (283 K):

 ΔS is positive → Spontaneous
Freezing of Water:
 Freezing is the reverse of melting.
 At -10°C, freezing is spontaneous.
 At 10°C, freezing is nonspontaneous.

SUMMARY
 1. Spontaneity depends on entropy (ΔS) and Gibbs free energy (ΔG).
2. Entropy (S) increases with disorder and temperature.
3. The Second Law of Thermodynamics states that all spontaneous processes
increase the universe's entropy.
4. The Third Law of Thermodynamics states that at absolute zero, entropy is zero.
5. ΔS can be calculated using standard molar entropies.
6. Gibbs free energy (ΔG) determines spontaneity:
o ΔG < 0 → Spontaneous

o ΔG > 0 → Nonspontaneous

o ΔG = 0 → Equilibrium

7. Temperature affects spontaneity, and some reactions may only be spontaneous at

specific temperatures.

Chemical Equilibrium and Le Chatelier’s Principle

Chemical Equilibrium
Chemical equilibrium is a state in a reversible reaction where the rates of the forward and
reverse reactions are equal, leading to no net change in the concentrations of reactants and
products over time. Although the reaction continues at the molecular level, overall
concentrations remain constant.
Reversible Reactions
Reversible reactions proceed in both forward and reverse directions. At the beginning, the
forward reaction is faster due to a higher concentration of reactants. As the reaction
progresses, the forward rate slows while the reverse rate increases. Eventually, equilibrium is
reached when both rates are equal.
Dynamic Equilibrium
Dynamic equilibrium means that while the reaction continues to occur, the concentrations of
reactants and products remain unchanged because their formation and consumption occur at
the same rate.
Types of Equilibrium
1. Fast Equilibrium: Some reactions reach equilibrium quickly, such as:
o Acid-base reactions (e.g., HCl + NaOH → H₂O + NaCl)

o Ionization of weak acids and bases (e.g., Acetic acid in water)

o Gas-phase reactions at high temperatures (e.g., N₂ + 3H₂ ⇌ 2NH₃)

2. Slow Equilibrium: Some reactions take a long time to reach equilibrium, such as:
o Solid-state reactions (e.g., Iron reacting with oxygen to form rust)

o Reactions with high activation energies

Irreversible Reactions
Some reactions only proceed in one direction, meaning reactants are completely converted to
products with no significant reverse reaction. Examples include:
  Combustion reactions (e.g., CH₄ + 2O₂ → CO₂ + 2H₂O)
 Explosions
 Precipitation reactions (e.g., AgNO₃ + NaCl → AgCl↓ + NaNO₃)

The equilibrium constant (K) is a numerical value that expresses the ratio of product concentrations to
reactant concentrations at equilibrium for a given chemical reaction. It indicates the extent to which a
reaction proceeds before reaching equilibrium and is fundamental in predicting reaction behavior.

General Expression for Equilibrium Constant (K)

For a reversible reaction:

The equilibrium constant is given by:

where:

 [C], [D], [A], and [B] are the equilibrium concentrations of the substances.
 a, b, c, and d are the stoichiometric coefficients from the balanced chemical equation.

1. Kc (Concentration-Based Equilibrium Constant)

o Used when reactants and products are in solution (mol/L).
o Expressed in terms of molar concentrations.

Interpreting K Values

 K >> 1 → The reaction favors products at equilibrium (mostly products present).

 K << 1 → The reaction favors reactants at equilibrium (mostly reactants present).
 K ≈ 1 → Significant amounts of both reactants and products are present at equilibrium.

The equilibrium constant in terms of partial pressure (Kp) is used for gaseous reactions and is expressed
using the partial pressures of reactants and products. It is related to the concentration-based equilibrium
constant (Kc) but specifically applies when gases are involved.

General Formula for Kp

For a general gaseous reaction:

The equilibrium constant in terms of partial pressure is:

where:

 PA,PB,PC,PDP_A, P_B, P_C, P_D are the equilibrium partial pressures of the gases (in
atm, bar, or other pressure units).
 a, b, c, d are the stoichiometric coefficients from the balanced equation.

Relation Between Kp and Kc

Kp and Kc are related by the equation:

Kp=Kc(RT)ΔnK_p = K_c (RT)^{\Delta n}

where:

 R = 0.0821 L·atm/(mol·K) (ideal gas constant).

 T = Temperature in Kelvin (K).
 Δn = Change in the number of moles of gas (moles of gaseous products - moles of
gaseous reactants).

When to Use Kp vs. Kc

 Use Kp when working with partial pressures of gases.

 Use Kc when working with concentrations (Molarity, M).

The equilibrium constant (K) is a fundamental concept in chemical equilibrium that depends on several
important considerations:

1. Temperature Dependence: The equilibrium constant is highly sensitive to temperature changes.

According to the Van't Hoff equation, an increase in temperature shifts the equilibrium position
depending on whether the reaction is exothermic or endothermic. For an exothermic reaction
(ΔH<0), increasing the temperature decreases KK because the reaction shifts toward the reactants.
Conversely, for an endothermic reaction (ΔH>0), increasing the temperature increases K as the
equilibrium shifts toward the products. This dependence arises because temperature affects the
relative stability of reactants and products.
2. Pure Solids and Liquids: In equilibrium expressions, the concentrations of pure solids and pure
liquids are not included. This is because their concentrations remain constant and do not affect the
equilibrium position. Instead, equilibrium expressions only include gaseous and aqueous species. For
example, in the reaction:

3. Units of the Equilibrium Constant: The units of KK depend on how the equilibrium expression is
written. For equilibrium constants expressed in terms of concentration (Kc), the units vary depending
on the reaction's stoichiometry. If the sum of the stoichiometric coefficients of products and reactants
is equal, Kc is dimensionless. Otherwise, its units depend on the molar concentration raised to the
appropriate power. For equilibrium constants expressed in terms of partial pressures (Kp), the units
 also depend on the reaction’s stoichiometry and are usually given in atm. However, in
thermodynamic expressions, equilibrium constants are often written in a dimensionless form by
using activities instead of concentrations or pressures.

Le Chatelier’s Principle
Le Chatelier’s Principle states that if an external stress (change in concentration, pressure, or
temperature) is applied to a system at equilibrium, the system will shift in a direction that
counteracts the disturbance.
Factors Affecting Equilibrium
1. Change in Concentration:
o Increasing reactant concentration shifts equilibrium to the right (favoring
products).
o Increasing product concentration shifts equilibrium to the left (favoring
reactants).
2. Change in Pressure (for gaseous reactions):
o Increasing pressure shifts equilibrium toward the side with fewer gas molecules.

o Decreasing pressure shifts equilibrium toward the side with more gas molecules.

3. Change in Temperature:
o For an exothermic reaction (ΔH < 0), increasing temperature shifts equilibrium
to the left.
o For an endothermic reaction (ΔH > 0), increasing temperature shifts
equilibrium to the right.
4. Effect of Catalysts:
o A catalyst speeds up both the forward and reverse reactions equally, allowing
equilibrium to be reached faster but does not shift the equilibrium position.

The reaction quotient (Q) is a mathematical expression that determines the relative amounts of reactants
and products in a chemical reaction at any given point in time. It is similar in form to the equilibrium
constant (K), but while K is calculated using equilibrium concentrations, Q is calculated using initial or non-
equilibrium concentrations. By comparing Q to K, we can predict the direction in which a reaction will
proceed to reach equilibrium.

Formula for Reaction Quotient (Q)

Reaction Quotient (Q)
Definition
 The reaction quotient (Q) is a measure of the relative amounts of products and
reactants present in a reaction at any given time.
 It is used to determine whether a reaction is at equilibrium and to predict the direction
in which it will shift.
 Q can be calculated for a reaction even when it is not at equilibrium.
For a general reaction:

The reaction quotient is expressed as:

where:

 [C], [D], [A], and [B] are the concentrations (or partial pressures for gases) at a given
moment.
 a, b, c, and d are the stoichiometric coefficients from the balanced equation.

How Q Changes Over Time

 The expression for Q is the same as for the equilibrium constant (K), but the value of Q
changes as the reaction proceeds.
 If the system is not yet at equilibrium, the value of Q will continuously change until it
reaches K.
 Regardless of the initial concentrations, the system will always react to attain
equilibrium.

Comparing Q and K: Predicting Reaction Direction

1. If Q = K → The system is at equilibrium, and no net change occurs.

2. If Q < K → The reaction shifts forward (right) to produce more products and reach
equilibrium.
3. If Q > K → The reaction shifts backward (left) to produce more reactants and reach
equilibrium.

Applications of Reaction Quotient

 Determining Reaction Progress: Helps in assessing how far a reaction is from

equilibrium.
 Predicting Precipitation: In solubility equilibria, comparing Q with Ksp (solubility
product constant) determines whether a precipitate will form.
 Controlling Industrial Reactions: Chemical engineers use Q to optimize reaction
conditions in manufacturing processes.

Acids and Bases: Definition, Properties, and Theories

Acids are substances that donate protons (H⁺), increase hydrogen ion concentration in a solution, or
accept electron pairs depending on the acid definition being used. They typically have a sour taste, can
corrode metals, and turn blue litmus paper red.

Acids and bases are fundamental chemical substances that play a key role in various chemical reactions,
biological processes, and industrial applications. They can be defined using different theories, each
providing a unique perspective on their behavior.
1. Theories of Acids and Bases
a. Arrhenius Definition (1884)

 Acid: A substance that increases the concentration of H⁺ (or H₃O⁺) ions in aqueous
solution.

 Base: A substance that increases the concentration of OH⁻ (hydroxide ions) in

aqueous solution.

 Limitation: This theory applies only to aqueous solutions.

b. Brønsted-Lowry Definition (1923)

 Acid: A proton (H+ H⁺) donor.

 Base: A proton (H+ H⁺) acceptor.

 Introduces conjugate acid-base pairs:

o Acid → Loses H⁺ → Becomes conjugate base.
o Base → Gains H⁺ → Becomes conjugate acid.

c. Lewis Definition (1923)

 Acid: An electron pair acceptor.

 Base: An electron pair donor.

 This definition extends beyond aqueous solutions and explains complex formation in
chemistry.
2. Properties of Acids and Bases
Acids

 Taste: Sour (e.g., vinegar, citrus fruits).

 pH: Less than 7.
 Conductivity: Electrolytes in solution.

 Reaction with bases: Neutralization reaction forms salt and water.

Bases

 Taste: Bitter.
 pH: Greater than 7.
 Feel: Slippery (like soap).
 Conductivity: Electrolytes in solution.
 Reaction with acids: Neutralization reaction forms salt and water.
3. Strength of Acids and Bases
Strong Acids (completely ionize in water)

Weak Acids (partially ionize in water)

Strong Bases (completely dissociate in water)

Weak Bases (partially ionize in water)

4. pH and pOH Scale


pH Range Nature of Solution
pH < 7 Acidic
pH = 7 Neutral
pH > 7 Basic

5. Acid-Base Neutralization and Buffers