Heat Capacity at Constant Volume and Pressure

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Core Idea

Heat capacity is the amount of heat required to raise temperature by one unit. At constant volume (Cv), all heat goes into internal energy: Q_v = nCvΔT. At constant pressure (Cp), heat also does flow work: Q_p = nCpΔT. These are different for the same substance and relate through the gas constant.

Explainer

From the first law of thermodynamics, ΔU = Q − W: the internal energy changes by the heat added minus the work done by the system. When you heat a gas, where does the energy go? The answer depends on whether the gas is free to expand — and this is the essential distinction between Cv and Cp.

At constant volume, the container walls prevent expansion, so no PdV work is done (W = 0). All the heat goes directly into internal energy: Q_v = ΔU = nCv ΔT. The molar heat capacity at constant volume, Cv, is defined precisely by this: Cv = (1/n)(∂U/∂T)_V. For a monatomic ideal gas, the only internal energy is translational kinetic energy — 3/2 RT per mole from the equipartition theorem — so Cv = 3R/2 ≈ 12.5 J/(mol·K). The temperature rise is entirely due to faster molecular motion; no energy is "wasted" on expansion.

At constant pressure, the gas expands as it warms. For an ideal gas, ΔV = nRΔT/P, so the system does work W = PΔV = nRΔT on its surroundings. To achieve the same temperature rise as in the constant-volume case, you must supply that extra work on top of the internal energy increase: Q_p = ΔU + W = nCv ΔT + nR ΔT = n(Cv + R) ΔT. This gives Cp = Cv + R — the Mayer relation. From your study of enthalpy H = U + PV, this has an elegant interpretation: at constant pressure, Q = ΔH = nCp ΔT, so Cp = (1/n)(∂H/∂T)_P. Enthalpy is the natural thermodynamic potential for constant-pressure processes precisely because it already includes the PV work term.

The ratio γ = Cp/Cv = (Cv + R)/Cv has wide physical significance. For a monatomic ideal gas, γ = 5/3. For diatomic gases like N₂ and O₂ at room temperature, the two rotational degrees of freedom contribute, making Cv = 5R/2 and γ = 7/5. At higher temperatures, vibrational modes activate, raising Cv further and driving γ toward 1. The physical content is this: a gas with more internal degrees of freedom absorbs heat more "efficiently" — temperature rises more slowly because the energy distributes among more modes. Measuring Cv or Cp thus probes the internal structure of a molecule, and the temperature-dependence of γ charts which molecular degrees of freedom become thermally accessible at each temperature.

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 Pressure

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