Topics

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Physical Equilibrium

Overview

Physical equilibrium occurs when two physical states or processes coexist with no observable macroscopic change, although microscopic changes continue. In a closed system, evaporation and condensation, melting and freezing, or sublimation and deposition can occur at equal rates. This dynamic nature is central to NCERT and NEET questions. Examples include ice and water at 273 K, saturated salt solution, water vapour in a closed container, and iodine crystals with iodine vapour. Important measurable ideas are vapour pressure, saturation, phase boundaries, and the effect of temperature and pressure. Physical equilibrium helps students understand why equilibrium does not mean stopping, but equal opposing rates.

Key Points6
  • 1Physical equilibrium involves no chemical composition change.
  • 2Saturated solution represents solute-solid equilibrium with dissolved solute.
  • 3Boiling occurs when vapour pressure equals external pressure.
  • 4Phase diagrams show stable regions of solid, liquid, and gas.
  • 5Dynamic equilibrium is established faster when surface area or temperature is higher.
  • 6For pure substances, equilibrium conditions are fixed at a given pressure and temperature.
Memory Tricks2

Dynamic Means Doing

Remember: equilibrium is not dead still. It is a busy balance where both opposite processes keep doing work at equal rates.

Closed Container Rule

For liquid-vapour equilibrium, think 'cap it to trap it' because escaping vapour prevents equilibrium in an open vessel.

Examples2

Water Bottle Example

In a closed water bottle, some water evaporates and some vapour condenses. After some time, the level appears unchanged because both rates become equal.

Saturated Sugar Solution

Undissolved sugar and dissolved sugar remain in equilibrium when dissolution and crystallization occur at equal rates.

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Common Mistakes2

Thinking Equilibrium Means No Motion

At equilibrium, molecules still move and processes continue. Only the rates and macroscopic properties become constant.

Confusing Evaporation with Boiling

Evaporation can occur at any temperature, while boiling requires vapour pressure to equal external pressure.

Formula Cards2
Boiling Condition

A liquid boils when its vapour pressure becomes equal to the external pressure.

Variables

P_vapour=

Vapour pressure of the liquid

P_external=

External atmospheric or applied pressure

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2

Chemical Equilibrium and Law of Mass Action

Overview

Chemical equilibrium is reached in a reversible reaction when the rate of forward reaction becomes equal to the rate of backward reaction. Reactants and products continue to interconvert, but their concentrations become constant with time. According to the law of mass action, the rate of a chemical reaction is proportional to the product of active masses of reactants raised to their stoichiometric powers. For a general reaction, this leads to the equilibrium constant expression. NEET frequently tests writing Kc correctly, excluding pure solids and liquids, interpreting equilibrium composition, and understanding that equilibrium can be reached from either direction in a closed system.

Key Points6
  • 1Equilibrium is dynamic and molecular collisions continue.
  • 2Law of mass action connects concentration and reaction rate.
  • 3Stoichiometric coefficients become powers in Kc expression.
  • 4The value of K depends only on temperature for a given reaction.
  • 5Large K means product-favoured equilibrium; small K means reactant-favoured equilibrium.
  • 6Chemical equilibrium requires a closed system for gases and volatile substances.
Memory Tricks2

Products on Top

For Kc, always place products in numerator and reactants in denominator: P over R.

Solid-Liquid Silent

Pure solids and pure liquids are silent in K expressions because their active masses are constant.

Examples2

Haber Process

N2 + 3H2 ⇌ 2NH3 is a classic reversible reaction where ammonia formation and decomposition occur simultaneously at equilibrium.

Dissociation of PCl5

PCl5 ⇌ PCl3 + Cl2 is frequently used in NEET to calculate Kc, Kp, and degree of dissociation.

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Common Mistakes2

Using Initial Concentrations in Kc

Kc must be calculated using equilibrium concentrations, not initial concentrations.

Assuming Equal Concentrations

Equilibrium means equal rates, not equal amounts of reactants and products.

Formula Cards2
Equilibrium Constant Kc

Gives concentration-based equilibrium constant for a homogeneous reaction.

Variables

[A], [B], [C], [D]=

Equilibrium molar concentrations

a, b, c, d=

Stoichiometric coefficients

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3

Equilibrium Constant Kc, Kp and Reaction Quotient

Overview

The equilibrium constant measures how far a reversible reaction proceeds before equilibrium is established. Kc uses molar concentrations, while Kp uses partial pressures for gaseous reactions. Their relation depends on the change in moles of gaseous species, Δn. The reaction quotient Q has the same expression as K but uses concentrations or pressures at any instant, not necessarily equilibrium. Comparing Q with K predicts the direction of reaction. This topic is very important for NEET numerical problems involving ICE tables, partial pressure, degree of dissociation, and deciding whether a reaction moves forward or backward.

Key Points6
  • 1Kc and Kp are dimensionless in modern thermodynamics, though units may appear in older numerical treatment.
  • 2Only gaseous species enter Kp expression.
  • 3ICE tables help organize initial, change, and equilibrium amounts.
  • 4For reverse reaction, K_reverse = 1 / K_forward.
  • 5If a reaction is multiplied by n, new K = K^n.
  • 6If reactions are added, total K is product of individual K values.
Memory Tricks2

Q is Question, K is Known Answer

Compare the current question Q with the equilibrium answer K to decide which direction the reaction must move.

Delta n is Gas Only

For Kp = Kc(RT)^Δn, count only gaseous moles. Ignore solids, liquids, and aqueous species.

Examples2

PCl5 Dissociation

For PCl5(g) ⇌ PCl3(g) + Cl2(g), Δn = 2 - 1 = 1, so Kp = KcRT.

No Change Case

For H2(g) + I2(g) ⇌ 2HI(g), Δn = 0, so Kp = Kc.

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Common Mistakes2

Counting All Species in Δn

Δn includes only gaseous species. Including solids or liquids gives wrong Kp-Kc relation.

Reversing Q Direction

If Q is less than K, products are deficient, so the reaction goes forward.

Formula Cards3
Kp-Kc Relation

Relates pressure equilibrium constant to concentration equilibrium constant for gaseous reactions.

Variables

Kp=

Equilibrium constant in terms of partial pressure

Kc=

Equilibrium constant in terms of molar concentration

R=

Gas constant

T=

Absolute temperature in kelvin

Δn=

Moles of gaseous products minus gaseous reactants

Reaction Quotient

Same form as Kc but calculated at any instant to predict reaction direction.

Variables

Qc=

Reaction quotient using concentration

[A], [B], [C], [D]=

Instantaneous molar concentrations

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4

Le Chatelier Principle and Factors Affecting Equilibrium

Overview

Le Chatelier principle states that when a system at equilibrium is disturbed by changing concentration, pressure, volume, or temperature, the system shifts in a direction that reduces the disturbance. It is a prediction tool for equilibrium shifts and industrial optimization. Adding reactant usually shifts equilibrium forward; increasing pressure favours the side with fewer gaseous moles; increasing temperature favours the endothermic direction. A catalyst does not shift equilibrium; it only helps equilibrium reach faster by lowering activation energy of both directions equally. NEET commonly asks conceptual questions on Haber process, Contact process, colour changes, and pressure-volume effects.

Key Points6
  • 1Le Chatelier principle predicts direction, not exact equilibrium composition.
  • 2Pressure affects only gaseous equilibria with unequal gaseous moles.
  • 3If Δn_gas = 0, pressure or volume change has no shift effect.
  • 4Temperature changes can change the numerical value of K.
  • 5Catalyst lowers activation energy for both forward and reverse reactions equally.
  • 6Industrial processes use compromise conditions for yield and rate.
Memory Tricks2

Equilibrium Pushes Back

Le Chatelier is like a spring: push the system, and it pushes back to reduce the effect.

Heat as a Species

Write heat on product side for exothermic and reactant side for endothermic reactions to predict temperature shifts.

Examples2

Haber Process

N2 + 3H2 ⇌ 2NH3 has fewer gas moles on product side, so high pressure favours ammonia formation.

Brown NO2 Equilibrium

2NO2 ⇌ N2O4 is exothermic in forward direction. Cooling favours colourless N2O4, while heating favours brown NO2.

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Common Mistakes2

Saying Catalyst Increases Yield

Catalyst increases rate of reaching equilibrium, not equilibrium yield.

Applying Pressure Rule to Liquids

Pressure-volume shifts are significant mainly for gaseous equilibria.

Formula Cards2
Temperature Dependence of K

Heat behaves like a product in exothermic reactions, so adding heat shifts equilibrium backward.

Variables

T=

Absolute temperature

K=

Equilibrium constant

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5

Ionic Equilibrium, Electrolytes and Ostwald Dilution Law

Overview

Ionic equilibrium deals with reversible ionization of weak electrolytes in aqueous solution. Strong electrolytes almost completely ionize, while weak electrolytes partially ionize and establish equilibrium between unionized molecules and ions. Degree of ionization, α, represents the fraction ionized and depends on concentration, dilution, temperature, and common ions. Ostwald dilution law relates the dissociation constant of a weak electrolyte with concentration and α. Dilution increases ionization of weak electrolytes, while addition of a common ion suppresses ionization. These concepts form the base for pH, buffers, salt hydrolysis, and solubility product problems in NEET.

Key Points6
  • 1Ionic equilibrium applies to aqueous weak electrolytes.
  • 2For weak acid HA, Ka = Cα²/(1-α).
  • 3If α is very small, Ka ≈ Cα².
  • 4Common ion effect is a direct application of Le Chatelier principle.
  • 5Ionization increases as concentration decreases.
  • 6The dissociation constant depends on temperature.
Memory Tricks2

Dilution Dissociates

For weak electrolytes, remember D-D: Dilution increases Dissociation.

Common Ion Compresses Ionization

A common ion is like crowding the product side, so the equilibrium shifts back.

Examples2

Acetic Acid Dilution

When CH3COOH is diluted, its percent ionization increases because the equilibrium shifts toward more ions.

Adding Sodium Acetate

Adding CH3COONa to CH3COOH supplies CH3COO- and suppresses acetic acid ionization.

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Common Mistakes2

Applying Ostwald Law to Strong Electrolytes

Ostwald dilution law is meant for weak electrolytes, not strong acids or salts that ionize almost completely.

Forgetting Approximation Condition

Use 1 - α ≈ 1 only when α is very small, generally less than about 0.05.

Formula Cards3
Degree of Ionization

Fraction of electrolyte molecules that dissociate into ions.

Variables

α=

Degree of ionization or dissociation

Ostwald Dilution Law for Weak Acid

Relates acid dissociation constant to concentration and degree of ionization.

Variables

Ka=

Acid dissociation constant

C=

Initial molar concentration

α=

Degree of ionization

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6

Acids, Bases, pH, pKa and pKb

Overview

Acids and bases can be understood through Arrhenius, Bronsted-Lowry, and Lewis concepts. Arrhenius acids produce H+ in water and bases produce OH-. Bronsted acids donate protons, while Bronsted bases accept protons. Lewis acids accept electron pairs and Lewis bases donate electron pairs, making this the broadest concept. pH measures hydrogen ion concentration and is crucial for NEET numericals. Strong acids and bases ionize almost completely, whereas weak acids and bases require Ka or Kb. pKa and pKb are logarithmic strength indicators: smaller pKa means stronger acid, and smaller pKb means stronger base.

Key Points6
  • 1Lewis theory includes reactions without proton transfer.
  • 2Water is amphoteric because it can donate or accept H+.
  • 3Strong acid pH is calculated directly from concentration if fully ionized.
  • 4Weak acid pH requires Ka and approximation or quadratic solution.
  • 5pH scale is logarithmic: one unit change means tenfold change in [H+].
  • 6At 298 K, neutral solution has pH = 7 because [H+] = [OH-] = 10^-7 M.
Memory Tricks3

BL: Base Likes H+

In Bronsted-Lowry theory, a base likes and accepts H+, while acid donates H+.

Lewis Lends Pair

Lewis base lends an electron pair; Lewis acid accepts it.

pH Power

Each pH unit is a power of 10 change in hydrogen ion concentration.

Examples2

Strong Acid pH

For 0.01 M HCl, [H+] = 10^-2 M, so pH = 2.

Lewis Acid Example

BF3 acts as a Lewis acid because boron has an incomplete octet and accepts an electron pair from NH3.

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Common Mistakes2

Forgetting Logarithmic Scale

pH 3 is ten times more acidic than pH 4, not just one unit more acidic.

Using pH + pOH = 14 at All Temperatures

pH + pOH = 14 strictly applies at 298 K because Kw changes with temperature.

Formula Cards5
pH

Measures acidity of a solution using hydrogen ion concentration.

Variables

pH=

Negative logarithm of hydrogen ion concentration

[H+]=

Molar concentration of hydrogen ions

pOH

Measures basicity using hydroxide ion concentration.

Variables

pOH=

Negative logarithm of hydroxide ion concentration

[OH-]=

Molar concentration of hydroxide ions

Ionic Product of Water

At 298 K, Kw = 1.0 × 10^-14.

Variables

Kw=

Ionic product of water

[H+]=

Hydrogen ion concentration

[OH-]=

Hydroxide ion concentration

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7

Hydrolysis of Salts and pH of Salt Solutions

Overview

Salt hydrolysis occurs when ions of a salt react with water to produce H+ or OH-, making the solution acidic or basic. Salts of strong acid and strong base do not hydrolyse appreciably and give neutral solution. Salts of strong acid and weak base produce acidic solutions because the cation hydrolyses. Salts of weak acid and strong base produce basic solutions because the anion hydrolyses. Salts of weak acid and weak base require comparison of Ka and Kb. NEET often asks direct pH nature, hydrolysis constant, and relation between hydrolysis and conjugate acid-base strength.

Key Points6
  • 1Hydrolysis is reverse of neutralization for salt ions.
  • 2Conjugate base of weak acid is basic and hydrolyses.
  • 3Conjugate acid of weak base is acidic and hydrolyses.
  • 4NaCl solution is neutral because Na+ and Cl- do not hydrolyse significantly.
  • 5NH4Cl solution is acidic due to NH4+ hydrolysis.
  • 6CH3COONa solution is basic due to acetate ion hydrolysis.
Memory Tricks2

Strong Parents, Neutral Child

A salt from strong acid and strong base is neutral because both parent ions are too weak to hydrolyse.

Weak Acid Salt is Basic

If the acid parent is weak, its conjugate base is strong enough to take H+ from water, giving OH-.

Examples2

NH4Cl is Acidic

NH4+ donates H+ to water to form H3O+, so ammonium chloride solution has pH less than 7.

Sodium Acetate is Basic

CH3COO- accepts H+ from water, leaving OH-, so sodium acetate solution has pH greater than 7.

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Common Mistakes2

Calling Every Salt Neutral

Only salts of strong acid and strong base are neutral. Many salts hydrolyse and change pH.

Ignoring Ka versus Kb for Weak-Weak Salts

For weak acid-weak base salts, compare Ka and Kb to decide acidic, basic, or neutral nature.

Formula Cards4
Hydrolysis Constant for Salt of Weak Acid and Strong Base

Used for anion hydrolysis such as CH3COO- in sodium acetate.

Variables

Kh=

Hydrolysis constant

Kw=

Ionic product of water

Ka=

Dissociation constant of weak acid

Hydrolysis Constant for Salt of Strong Acid and Weak Base

Used for cation hydrolysis such as NH4+ in ammonium chloride.

Variables

Kh=

Hydrolysis constant

Kw=

Ionic product of water

Kb=

Dissociation constant of weak base

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8

Buffer Solutions and Henderson Equation

Overview

A buffer solution resists change in pH when small amounts of acid or base are added. Acidic buffers contain a weak acid and its salt with a strong base, such as CH3COOH and CH3COONa. Basic buffers contain a weak base and its salt with a strong acid, such as NH4OH and NH4Cl. Buffer action occurs due to the common ion effect: added H+ or OH- is consumed by buffer components. Henderson-Hasselbalch equations allow quick pH calculation. Buffers are important in biological systems like blood, in analytical chemistry, and in NEET problems involving pKa, pKb, and concentration ratios.

Key Points6
  • 1Buffers resist pH change but do not keep pH absolutely constant under unlimited acid or base.
  • 2The salt supplies conjugate ion needed to neutralize added acid or base.
  • 3Dilution changes buffer capacity but pH changes only slightly if ratio remains same.
  • 4Blood buffer mainly involves carbonic acid and bicarbonate ions.
  • 5Henderson equation uses concentration ratio, so units cancel.
  • 6A good buffer has pKa close to desired pH.
Memory Tricks2

Buffer Has Both Shield and Sponge

The weak acid/base pair acts like a shield: one part absorbs H+, the other absorbs OH-.

Salt Over Acid

For acidic buffer, remember pH has salt over acid: pH = pKa + log S/A.

Examples2

Acetate Buffer

A mixture of CH3COOH and CH3COONa maintains pH near the pKa of acetic acid.

Blood Buffer

The H2CO3/HCO3- system helps maintain blood pH around 7.4.

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Common Mistakes2

Using Strong Acid and Strong Base as Buffer

A buffer needs a weak acid/base and its conjugate salt. Strong acid-base mixtures do not provide buffer action.

Forgetting pOH in Basic Buffer

For basic buffer, first calculate pOH, then convert using pH = 14 - pOH at 298 K.

Formula Cards2
Henderson Equation for Acidic Buffer

Calculates pH of weak acid and conjugate base buffer.

Variables

pH=

Acidity measure of buffer

pKa=

Negative logarithm of acid dissociation constant

[salt]=

Concentration of conjugate base salt

[acid]=

Concentration of weak acid

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9

Solubility Product, Precipitation and Common Ion Effect

Overview

Solubility product, Ksp, is the equilibrium constant for dissolution of a sparingly soluble salt in water. When a salt such as AgCl dissolves, a dynamic equilibrium exists between solid salt and its ions in solution. The ionic product is calculated using actual ion concentrations at any instant. If ionic product is less than Ksp, no precipitate forms; if equal, the solution is saturated; if greater, precipitation occurs. Common ion effect decreases solubility by shifting dissolution equilibrium backward. This topic is highly important for NEET problems on precipitation, salt solubility, group separation, and comparing Ksp values.

Key Points6
  • 1Ksp is a constant at a given temperature.
  • 2Molar solubility must be converted using stoichiometry before writing Ksp.
  • 3For AB salt, Ksp = s² if solubility is s.
  • 4For AB2 salt, Ksp = 4s³.
  • 5Selective precipitation depends on different Ksp values.
  • 6Adding a common ion shifts equilibrium toward undissolved solid.
Memory Tricks2

Qsp Decides Precipitate

Think of Qsp as current ion crowding. If crowding exceeds Ksp capacity, the salt precipitates.

Common Ion Crashes Solubility

Adding an ion already present pushes the dissolved salt back into solid form.

Examples2

AgCl Precipitation

Mixing AgNO3 and NaCl gives Ag+ and Cl-. If [Ag+][Cl-] exceeds Ksp of AgCl, a white precipitate forms.

Group Analysis

Selective precipitation of metal ions is based on differences in Ksp values of their salts.

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Common Mistakes2

Comparing Ksp Without Stoichiometry

You can directly compare solubility using Ksp only for salts with the same ion ratio.

Forgetting Powers in Ksp

For AB2, [B-] = 2s, so Ksp = s(2s)^2 = 4s^3, not s^3.

Formula Cards3
Ksp for AB Type Salt

Used when one mole of salt gives one cation and one anion.

Variables

Ksp=

Solubility product constant

s=

Molar solubility of AB

Ksp for AB2 Type Salt

Stoichiometry must be included when ions are produced in unequal numbers.

Variables

Ksp=

Solubility product constant

s=

Molar solubility of AB2

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10

Formula Sheet, Quick Revision and NEET Mind Map

Overview

This topic collects the most exam-oriented formulas, decision rules, and NCERT concepts from the complete Equilibrium chapter. For NEET, students must rapidly connect physical equilibrium, chemical equilibrium, Le Chatelier principle, ionic equilibrium, pH calculations, buffer equations, hydrolysis, and solubility product. Most errors occur when students use initial concentration instead of equilibrium concentration, include solids in K expressions, forget Δn is only for gases, or apply pH formulas outside their conditions. The mind map helps revise the chapter as one connected system: equilibrium constants describe position, Q predicts direction, Le Chatelier predicts shift, and ionic equilibria explain pH, buffers, and precipitation.

Key Points6
  • 1Pure solids and liquids are excluded from K, Q, and Ksp expressions.
  • 2K changes only with temperature, not with catalyst or concentration.
  • 3Strong electrolytes ionize almost completely; weak electrolytes use equilibrium constants.
  • 4Common ion effect suppresses ionization and solubility.
  • 5For salt hydrolysis, identify parent acid and base first.
  • 6For buffer problems, identify whether pH or pOH equation is needed.
Memory Tricks2

K-Q-L-pH-Ksp Chain

Remember the chapter flow as K tells position, Q tells direction, Le Chatelier tells shift, pH tells acidity, and Ksp tells precipitation.

Products Over Reactants

Most equilibrium expressions begin with the same habit: products on top, reactants below, powers from coefficients.

Examples3

Fast Direction Check

If for a reaction K = 10 and Q = 2, products are deficient, so the reaction proceeds forward.

Fast Buffer Check

If [salt] = [acid] in an acidic buffer, pH = pKa because log 1 = 0.

Fast Ksp Check

If Ksp of AgCl is 1.8 × 10^-10 and [Ag+][Cl-] is 10^-8, precipitation occurs because Qsp > Ksp.

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Common Mistakes3

Mixing K and Q

K is only at equilibrium; Q is at any instant. Use Q for direction prediction.

Not Checking Approximation

Weak acid/base approximations should be verified when ionization is not very small.

Forgetting Temperature Dependence

Only temperature changes the equilibrium constant. Concentration and pressure change position but not K.

Formula Cards7
General Kc

Universal structure for concentration equilibrium constant.

Variables

Kc=

Concentration equilibrium constant

Kp-Kc

Use only for gaseous reactions.

Variables

Δn=

Gaseous product moles minus gaseous reactant moles

Water Ion Product

Central relation for pH and pOH calculations.

Variables

Kw=

Ionic product of water

pH Relations

Most used acid-base formulas in NEET.

Variables

[H+]=

Hydrogen ion concentration

[OH-]=

Hydroxide ion concentration

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Formula Sheet

10
Boiling Condition

A liquid boils when its vapour pressure becomes equal to the external pressure.

Variables

P_vapour=

Vapour pressure of the liquid

P_external=

External atmospheric or applied pressure

Relative Humidity

Used to compare actual water vapour present in air with the maximum possible vapour at that temperature.

Variables

actual vapour pressure=

Partial pressure of water vapour present

saturated vapour pressure=

Maximum vapour pressure of water at same temperature

Equilibrium Constant Kc

Gives concentration-based equilibrium constant for a homogeneous reaction.

Variables

[A], [B], [C], [D]=

Equilibrium molar concentrations

a, b, c, d=

Stoichiometric coefficients

Forward Rate

According to mass action for an elementary forward reaction, rate depends on active masses of reactants.

Variables

r_f=

Forward reaction rate

[A], [B]=

Active masses or molar concentrations

Kp-Kc Relation

Relates pressure equilibrium constant to concentration equilibrium constant for gaseous reactions.

Variables

Kp=

Equilibrium constant in terms of partial pressure

Kc=

Equilibrium constant in terms of molar concentration

R=

Gas constant

T=

Absolute temperature in kelvin

Δn=

Moles of gaseous products minus gaseous reactants

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NEET 2026Set 11MediumQ1

Given below are certain reactions. Identify the reaction for which Kp ≠ Kc.

NEET 2026Set 11EasyQ2

Phenolphthalein is used as an indicator for the titration of sodium hydroxide solution against a standard solution of oxalic acid. The colour change observed at alkaline pH close to the equivalence point is:

NEET 2026Set 11MediumQ3

At 298 K, a certain buffer solution contains equal concentrations of X⁻ and HX. K$_b$ for X⁻ is 10⁻¹⁰. What is the pH of this buffer solution?

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