Chemistry

Equilibrium
(One Shot)

Concepts Covered in the Class:

• Dynamic & Chemical Equilibrium

• Equilibrium Constants ( 𝐾𝑐 , 𝐾𝑝 ) & Reaction Quotient

(𝑄𝑐 )
• Thermodynamics of Equilibrium ( Δ𝐺 & Van't Hoff

Equation)
• L e-Chatelier's Principle & S ystem S hifts

• Theories of Acids and Bases

• p H S cal e, El ectrol ytes & O stw al d Dil ution L aw

• S al t Hydrol ysis & Buffer S ol utions
• S ol ubility Product ( 𝐾𝑠𝑝 ) & Indicators

The Paradox of Dynamic Equilibrium

• Dynamic equilibrium is a state of continuous, equal,

and opp osing activity, not a static p ause.

• F ormul a: Rate of forw ard reaction = Rate of backw ard

reaction at equilibrium.

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• Implication: Reactant and p roduct concentrations
become constant, but do not necessaril y equal each
other.

Concept 3: Law of Mass Action (LOMA)

• Active mass is the effective concentration
determining a reacting sp ecies' "p ulling strength".
• F ormul a: Rate of Forward ∝ [𝐴]𝑎 [𝐵]𝑏 and
Rate of Backward ∝ [𝐶]𝑐 [𝐷]𝑑

Concept 4: The Equilibrium Constant ( 𝐾𝑐 )

• Rep resents the ratio of rate constants for forw ard
and backw ard reactions.
[𝐶]𝑐 [𝐷]𝑑
• F ormul a: 𝐾𝑐 =
[𝐴]𝑎 [𝐵]𝑏

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• Implication: Onl y gases ( g) and aqueous ( aq) species
are incl uded; p ure solids (s) and l iquids ( l) are
ignored.

Concept 5: Pressure Enters the Chat ( 𝐾𝑝 )

• Adapted exclusivel y for gaseous reactions using
p artial pressure (individual p ressure exerted by a
singl e gas).
(𝑃𝐶 )𝑐 (𝑃𝐷 )𝑑
• F ormul a: 𝐾𝑝 =
(𝑃𝐴 )𝑎 (𝑃𝐵 )𝑏

Synthesis: The Δ𝑛𝑔 Decision Tree

• Rel ates 𝐾𝑝 and 𝐾𝑐 based on the change in gaseous
moles (Δ𝑛𝑔 ).
• F ormul a: 𝐾𝑝 = 𝐾𝑐 (𝑅𝑇)Δ𝑛𝑔
• Implication: If Δ𝑛𝑔 = 0, 𝐾𝑝 = 𝐾𝑐 ; if Δ𝑛𝑔 > 0, 𝐾𝑝 > 𝐾𝑐 ; if
Δ𝑛𝑔 < 0, 𝐾𝑝 < 𝐾𝑐 .

The Laws of K: Transformation Matrix

• Modifying a chemical equation mathematicall y al ters
its equilibrium constant.

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• K ey rul es: Reversing the reaction makes 𝐾 ′ = 1/𝐾;
mul tipl ying by factor 𝑥 makes 𝐾 ′ = (𝐾)𝑥 ; adding
equations makes 𝐾 ′ = 𝐾1 × 𝐾2 .

THE VAN'T HOFF EQUATION & REACTION

ENTHALPY
• Connects the equilibrium constant to temperature
and reaction enthalp y ( Δ𝐻).
Δ𝐻
• F ormul a: ln𝐾 = ln𝐴 −
𝑅𝑇
• Implication: Plotting ln𝐾𝑒𝑞 vs 1/𝑇 yiel ds a sl op e of
−Δ𝐻/𝑅, al lowing determination of exo/endothermic
nature.

Concept 7: Temperature - The Ultimate Rule

Breaker
• The equil ibrium constant ( 𝐾) is extremel y stubborn
and changes for onl y O NE variable: Temperature.
𝐾 Δ𝐻 𝑇 −𝑇
• F ormul a: log10 ( 2 ) = [ 2 1]
𝐾 1 2.303𝑅 𝑇 𝑇 1 2

• Implication: Increasing temperature increases 𝐾 for

endothermic reactions but decreases 𝐾 for exothermic
reactions.

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Q is the current state. K is the destination.
• The Reaction Quotient ( 𝑄𝑐 ) is cal cul ated at any
instant, w hil e 𝐾𝑐 is cal cul ated strictl y at equilibrium.
[𝐶]𝑐 [𝐷]𝑑
• F ormul a: 𝑄𝑐 = ( at time 𝑡)
[𝐴]𝑎 [𝐵]𝑏

• Implication: If 𝑄𝑐 < 𝐾𝑐 , the reaction shifts forw ard;

if 𝑄𝑐 > 𝐾𝑐 , it shifts backw ard to reach equilibrium.

DEGREE OF DISSOCIATION ( 𝛼)
• Measures the fraction of a substance that has
dissociated into ions or simpl er mol ecul es.
moles dissociated (𝑥)
• F ormul a: 𝛼 =
moles taken initially (𝐶)

UNIVERSAL RULE
• Defines how the degree of dissociation ( 𝛼) rel ates
to Vol ume ( 𝑉) and Pressure ( 𝑃).
• F ormul a: 𝛼 ∝ 𝑉 Δ𝑛𝑔 /𝑛𝑝(𝑔) and 𝛼 ∝ 𝑃−(Δ𝑛𝑔 /𝑛𝑝(𝑔) )

The Engine of Spontaneity: Δ𝐺 vs Δ𝐺 ∘

• Δ𝐺 rep resents the dynamic journey of a reaction,
w hile Δ𝐺 ∘ is a fixed standard benchmark.
• F ormul a: Δ𝐺 = Δ𝐺 ∘ + 𝑅𝑇ln𝑄

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• Implication: At equilibrium, Δ𝐺 = 0, simpl ifying the
equation to Δ𝐺 ∘ = −𝑅𝑇ln𝐾. Sp ontaneous reactions have
𝐾 > 1 and negative Δ𝐺 ∘ .

Le-Chartilier Principle
• If an equil ibrium system is disturbed, it shifts in a
direction that counteracts the change.
• Increasing reactant concentration or decreasing
volume ( increasing p ressure) shifts the system
forw ard or towards few er gas moles, resp ectivel y.
• Note: If Δ𝑛𝑔 = 0, changing p ressure or volume has no
effect.

The Arrhenius Baseline: Reactions Bound by Water

• Acids p roduce 𝐻 + or 𝐻3 𝑂+ in w ater.
• Bases produce 𝑂𝐻 − in w ater.

The Brønsted-Lowry Upgrade: The Universal

Proton Exchange
• Breaks free from the w ater requirement, defining
acids and bases by p roton ( 𝐻 + ) movement.
• A Proton Donor is an Acid, and a Proton Accep tor is
a Base.

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The Amphoteric Crossroads: Dual -Nature Molecules
• Amp hoteric species can act as both Brønsted Acids
and Bases.
• Exampl e: 𝐻𝑆𝑂4− can donate 𝐻 + to become 𝑆𝑂42− or
accep t 𝐻 + to become 𝐻2 𝑆𝑂4 .

The Lewis Concept defines acids and bases by

electron transfer
• L ewis Acid (Electrop hil e): A substance that can
ACCEPT a l one p air of electrons (e. g. , incomplete
octets like 𝐵𝐹3 , cations).
• L ewis Base (Nucl eop hil e): A substance that can
DO NATE a l one p air of el ectrons (e.g., neutral
molecules with l one p airs like 𝑁𝐻3 , anions).

Electrolyte: A substance which dissociates in

water to give ions.
• S trong Electrolytes dissociate 10 0 % ( 𝛼 = 1) into ions
using a one -way arrow.
• Weak El ectrolytes onl y p artiall y dissociate ( 𝛼 < 1)
and establish an equilibrium.

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Ostwald Dilution Law
• Governs the dissociation of weak el ectrol ytes,

connecting their ioniz ation constant to concentration

and degree of dissociation.

𝐶𝛼 2
• F ormul a: 𝐾𝑎 = ( Approximates to 𝛼 = √𝐾𝑎 /𝐶 for very
1−𝛼

w eak acids).

The Dissociation Dial: 5 factors affecting 𝛼

• The degree of dissociation increases with a higher

dielectric constant of the sol vent, higher

temperature, and greater dil ution.

• The "Common Ion Effect" supp resses and reduces the

degree of dissociation.

Ionic Product of Water ( 𝐾𝑤 )

• Rep resents the absolute product of ion

concentrations in p ure w ater.

• F ormul a: 𝐾𝑤 = [𝐻 + ][𝑂𝐻 − ] = 1.0 × 10−14 ( at 298𝐾).

• Implication: The Universal Link dictates 𝑝𝐾𝑤 = 𝑝𝐻 +

𝑝𝑂𝐻 = 14 at standard conditions.

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The pH Scale
• Characterises sol utions as Acidic (0 -6), Neutral ( 7),
or Basic (8 -14) at 25∘ 𝐶.

The Shifting Scale: Neutral is not always pH 7

• As temp erature increases, the pH scale p hysicall y
shrinks, and the neutrality point shifts dow nw ards.
• Neutrality is strictl y defined by equal concentrations
of [𝐻 + ] and [𝑂𝐻 − ], not the arbitrary number 7.

Application Protocol: Strong Acids vs. Strong

Bases
• Vital Prerequisite: Alw ays cal cul ate Normality ( 𝑁 =
𝑀 × n-factor) first.

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• F or strong acids, ap pl y directl y: 𝑝𝐻 = −log[𝐻 + ].
• F or strong bases, find 𝑝𝑂𝐻 = −log[𝑂𝐻 − ] first, then
cal cul ate 𝑝𝐻 = 14 − 𝑝𝑂𝐻.

pH of Diluted Acid or Diluted Base

• Dil ution adjustments can be cal cul ated using the
formul a 𝑀1 𝑉1 = 𝑀2 𝑉2 .
• Hack: Dil uting by 10 times drops [𝐻 + ] by 10x, causing

the p H to INCREASE by 1.

pH of Mixture of Strong Acids or Strong Base

• Mixing strong acids or strong bases combines their
ions without fighting, increasing the total ion count.
(𝑀1 𝑉1 +𝑀2 𝑉2 +⋯ )
• F ormul a: [𝐻 + ]mix =
(𝑉1 +𝑉2 +⋯ )

pH of Mixture of Strong Acids and Strong Base

• The comp onents neutral ize each other, and the l arger
equival ent dictates w hether the final sol ution is

acidic or basic.
|𝑁1 𝑉1 −𝑁2 𝑉2 |
• F ormul a: Resultant 𝑁 =
(𝑉1 +𝑉2 )

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Concept 1: pH of Weak Acid Mixtures
• The total [𝐻 + ] is derived from the combination of
their dissociation constants and concentrations.
• F ormul a: [𝐻 + ]Total = √𝐾𝑎1 𝐶1 + 𝐾𝑎2 𝐶2

Comparing Acidic Strength

• The rel ative strength of weak acids at equal
concentration is determined by the ratio of their
dissociation constants.
• F ormul a: Strength Ratio = √𝐾𝑎1 /𝐾𝑎2

Concept 2: The Conjugate Link

• The strength of an acid is inversel y p rop ortional to
the strength of its conjugate base.
• F ormul a: 𝐾𝑎 × 𝐾𝑏 = 𝐾𝑤 and 𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 𝑝𝐾𝑤

Salt Hydrolysis
• O ccurs w hen the cation or anion of a sal t reacts with
w ater to disrup t neutrality, forming acidic or basic
sol utions.

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• S trong comp onents yiel d stabl e "Sp ectator Ions" that
do not hydrol yse, w hile weak components yield
"Hydrol ysers".

Type 4: Salt of Weak Acid (W.A.) & Weak Base

(W.B.)
• The pH of this sal t typ e is indep endent of
concentration; dil uting it w ill not change its pH.
1
• F ormul a: 𝑝𝐻 = 7 + (𝑝𝐾𝑎 − 𝑝𝐾𝑏 )
2

Phase 2: The Solubility Product ( 𝐾𝑠𝑝 )

• Rep resents the ul timate mathematical l imit of
dissol ution for sp aringl y solubl e sal ts establishing
equilibrium.
• F ormul a: 𝐾𝑠𝑝 = 𝑥 𝑥 𝑦 𝑦 𝑆 (𝑥+𝑦) (w here 𝑥, 𝑦 are ion numbers,
and 𝑆 is mol ar sol ubility).

The Precipitation Threshold: 𝐾𝑖𝑝 vs 𝐾𝑠𝑝

• The Ionic Product ( 𝐾𝑖𝑝 ) acts as a gauge against the
cap acity limit ( 𝐾𝑠𝑝 ).
• Implication: If 𝐾𝑖𝑝 > 𝐾𝑠𝑝 , the solution is
sup ersaturated and precip itation occurs.

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ACIDIC BUFFER
• A system resisting p H change, made from a Weak
Acid and its Sal t with a S trong Base.
[Salt]
• F ormul a: 𝑝𝐻 = 𝑝𝐾𝑎 + log ( )
[Acid]

BASIC BUFFER
• A system resisting p H change, made from a Weak
Base and its Sal t with a S trong Acid.
[Salt]
• F ormul a: 𝑝𝑂𝐻 = 𝑝𝐾𝑏 + log ( ) (Remember to convert
[Base]

to p H via 14 − 𝑝𝑂𝐻).

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System Limits: Buffer Capacity ( 𝜙)
• A quantitative measure of a buffer's p hysical
robustness and how much chemical shock it can
absorb before failing.
Number of moles of acid/base added to 1L
• F ormul a: 𝜙 =
Change in pH

Indicators: The Messengers of Equivalence

• Extremel y w eak organic acids or bases that show
completel y different col ours in their undissociated
versus dissociated states.
• The human eye needs one form to be 10 x more
concentrated to see a change, making the universal
op erating range 𝑝𝐻 = 𝑝𝐾In ± 1.

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