Mayer's Relation: Cp − Cv = R

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heat-capacity ideal-gas thermodynamic-relations

Core Idea

Mayer's relation states that for an ideal gas, Cp − Cv = R (per mole). This arises because at constant pressure, part of the heat goes into work: Cp − Cv = P(∂V/∂T)_P = R. The difference reflects the flow work required for expansion at constant pressure.

Explainer

From your study of heat capacities and enthalpy, you have two distinct ways to heat a gas: hold the volume fixed, or hold the pressure fixed. At constant volume, all the heat you add goes directly into increasing the internal energy of the gas — raising the kinetic energy of the molecules. At constant pressure, the gas is free to expand, and when it expands it pushes on its surroundings, doing work. This means heating at constant pressure requires extra energy: you must supply both the thermal energy to raise the temperature and the mechanical energy to push back the atmosphere. Cₚ is always larger than Cᵥ for any substance, but for ideal gases the difference is exactly R, a universal constant.

The derivation makes this precise. The first law at constant pressure gives dQ = dU + PdV. By definition, Cₚ = (dQ/dT)_P = (dU/dT)_P + P(dV/dT)_P. The second term, P(∂V/∂T)_P, is the work term. For an ideal gas, PV = nRT, so P(∂V/∂T)_P = nR. Meanwhile, for an ideal gas, internal energy U depends only on temperature (not volume) — the molecules don't interact, so squeezing them together or spreading them apart doesn't change U. Therefore (∂U/∂T)_P = (∂U/∂T)_V = Cᵥ. Putting it together: Cₚ = Cᵥ + nR, or per mole, Cₚ − Cᵥ = R ≈ 8.314 J/(mol·K).

The physical picture is straightforward. When you add 1 mole of heat at constant volume, the temperature rises by ΔT = Q/Cᵥ. All of that heat went into molecular kinetic energy. When you add the same 1 mole of heat at constant pressure, the temperature rise is smaller: ΔT = Q/Cₚ < Q/Cᵥ. The "missing" temperature rise went into expansion work. For a monatomic ideal gas, Cᵥ = (3/2)R (three translational degrees of freedom, each contributing R/2 from the equipartition theorem), so Cₚ = (5/2)R. For a diatomic gas at room temperature, Cᵥ = (5/2)R (adding two rotational degrees of freedom), so Cₚ = (7/2)R. In both cases the difference is exactly R.

The ratio γ = Cₚ/Cᵥ = (Cᵥ + R)/Cᵥ appears throughout thermodynamics and is directly measurable. For monatomic gases γ = 5/3 ≈ 1.67; for diatomic gases γ = 7/5 = 1.40. This ratio sets the speed of sound: v = √(γRT/M), which is why sound travels faster in helium (γ = 5/3, M small) than in air (γ = 7/5). It also governs adiabatic processes: when a gas expands adiabatically, TV^{γ−1} = const and PV^γ = const. The steepness of the adiabatic curve on a PV diagram relative to the isothermal curve is exactly γ. Every time you calculate an adiabatic compression, an engine efficiency, or an acoustic velocity, Mayer's relation is quietly behind the γ that appears.

Mayer's relation holds exactly for ideal gases because the assumption (∂U/∂V)_T = 0 is exact for non-interacting molecules. For real gases, molecules do interact, and compressing them changes their potential energy as well as kinetic energy. The general relation is Cₚ − Cᵥ = −T(∂P/∂V)_T(∂V/∂T)²_P, which reduces to R for ideal gases but gives corrections for real gases near condensation or at high pressure. The departure from Cₚ − Cᵥ = R is itself a useful diagnostic: it measures intermolecular interactions through the internal pressure (∂U/∂V)_T, a term that vanishes for ideal gases and grows as conditions depart from ideality.

Practice Questions 5 questions

Prerequisite Chain

Counting to 10Counting to 20Understanding ZeroThe Number ZeroCounting to FiveOne-to-One CorrespondenceCombining Small Groups Within 5Addition Within 10Addition Within 20Two-Digit Addition Without RegroupingTwo-Digit Addition with RegroupingAddition Within 100Repeated Addition as MultiplicationMultiplication Facts Within 100Division as Equal SharingDivision as Grouping (Measurement Division)Division: Grouping (Repeated Subtraction) ModelDivision: Fair Sharing ModelDivision as Equal SharingDivision as GroupingBasic Division FactsDivision Facts Within 100Two-Digit by One-Digit DivisionDivision with RemaindersRemainders and Quotients in DivisionDivision Word ProblemsIntroduction to Long DivisionFactors and MultiplesPrime and Composite NumbersEquivalent FractionsRelating Fractions and DecimalsDecimal Place ValueReading and Writing DecimalsComparing and Ordering DecimalsAdding and Subtracting DecimalsMultiplying DecimalsDividing DecimalsDividing FractionsMixed Number ArithmeticOrder of OperationsInteger Order of OperationsVariable ExpressionsCombining Like TermsOne-Step EquationsTwo-Step EquationsSolving Multi-Step EquationsEquations with Variables on Both SidesAngle Pairs: Complementary, Supplementary, and VerticalParallel Lines and TransversalsCorresponding AnglesAlternate Interior AnglesTriangle Angle Sum TheoremExterior Angle TheoremTriangle Inequality TheoremSimilar Triangles: AA SimilaritySimilar Triangles: SSS and SAS SimilarityProportions in Similar TrianglesRight Triangle Trigonometry IntroductionTrigonometric Ratios ReviewRadian MeasureConverting Between Degrees and RadiansThe Unit CircleGraphing Sine and CosineGraphing Tangent and Reciprocal Trigonometric FunctionsDerivatives of Trigonometric FunctionsAntiderivativesIterated Integrals and Fubini's TheoremDouble Integrals in Cartesian CoordinatesDouble Integrals over Rectangular RegionsDouble Integrals in Polar CoordinatesDouble Integrals: Definition and SetupIterated Integrals and Fubini's TheoremDouble Integrals over Rectangular RegionsDouble Integrals over General RegionsApplications of Double Integrals: Area, Mass, and MomentsCenter of MassConservation of Linear MomentumElastic CollisionsInelastic CollisionsCoefficient of RestitutionCollision Analysis and Real-World ApplicationsTwo-Body Collisions in the Center-of-Mass FrameReduced Mass and Two-Body ProblemsKinematics in Two DimensionsProjectile MotionCircular Motion: KinematicsRotational KinematicsTorqueMoment of InertiaRotational Kinetic EnergyThe Work-Energy TheoremConservation of Mechanical EnergyFirst Law of ThermodynamicsHeat Capacity at Constant Volume and PressureMayer's Relation: Cp − Cv = R

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