Calorimetry

Calorimetry measures heat transfers. A calorimeter, a calibrated heat capacity and an accounting of unwanted heat transfer connect an observed temperature change to an energy balance, as in heat-engine calorimetry and heat-pump calorimetry.

The central idea is to measure a response that is easier to observe than the transfer itself: a known heat capacity turns a temperature change into an energy estimate. Mixing calorimetry can determine an unknown specific heat capacity, while a chemical reaction can be studied by measuring the response of its surroundings. The useful observable is a change in temperature, together with a stated thermodynamic system boundary; a hot object does not contain a separately conserved store of heat.

For a closed system with unchanged bulk kinetic energy and potential energy, let $Q_{\mathrm{in}}$ be net inward heat and $W_{\mathrm{on}}$ net inward work. The first law of thermodynamics givesIf the boundary includes a hot sample, receiving water and the participating vessel, their mutual heat transfer is internal. With no external input, the total storage change is minus the signed outward heat leakage, not the positive amount transferred from sample to water. A calorimeter calibration with an immersed resistor instead supplies electrical work across this boundary; Joule heating converts it into internal energy. Choosing only the receiving water as the boundary changes which transfers count as external.

The mechanical constraint decides which storage quantity the readout represents. For a closed system at fixed volume, with no other work, $Q_V=\Delta U$. At constant external pressure, with only expansion work $p\Delta V$, $Q_p=\Delta H$, where $H=U+pV$ is enthalpy. Thus the corresponding warming balances use heat capacity at constant volume or heat capacity at constant pressure. Electrical or shaft work must be included separately when present. These endpoint balances do not require the actual exchange to be a reversible thermodynamic process.

A covered cup open to atmospheric pressure approximately realizes the second constraint when escaping material is negligible. A sealed rigid reaction vessel realizes the first; its surrounding water, vessel and immersed parts form the calibrated receiver. The reaction's outward heat equals the receiver's gain only after losses and ignition input have been accounted for. The distinction concerns the reaction boundary, even if its receiver is open to atmospheric pressure.^[ref]

A historical quantitative result appears in James Prescott Joule's On the Mechanical Equivalent of Heat (1850): Table IX gives $772.692$ foot-pounds of mechanical work per warming of one pound of water by one degree Fahrenheit, with weighing reduced to vacuum. His final rounded statement specifies water between $55$ and $60$ degrees Fahrenheit. He acknowledged residual vibration and sound as possible upward bias. This is an original reported conversion result, not the definition of the modern joule; the apparatus and resting controls are described in Joule's paddle-wheel experiment.^[ref]

Use measured electrical energy input to calibrate or infer a thermal response. A heater's terminal electric potential difference and electric current determine the supplied energy; receiver heat capacity and losses must also be accounted for.

Infer an unknown heat capacity by thermal contact with a calibrated receiver and a measured common final temperature. The energy lost by hotter components equals the energy gained by colder components, with the calorimeter and surrounding heat transfer included. For appreciably varying heat capacities, use temperature integrals rather than constant $mc\Delta T$ terms.

differential scanning calorimetry measures differences in heat flow between sample and reference during a controlled temperature scan. Transition peaks can reveal cooperative lipid-chain melting, with scan rate, composition and reversibility affecting interpretation.

Mixing calorimetry determines heat capacities by bringing bodies at different temperatures into thermal contact. The striking feature is that the final temperature is a weighted arithmetic mean with heat capacities as weights, rather than weights given by mass. The vessel participates in the exchange even though it is not the sample being studied.

For a hot nonreacting sample of mass $m_x$, initial temperature $T_x$ and unknown specific heat capacity at constant pressure $c_x$, let receiving water have mass $m_w$, initial temperature $T_w$ and known specific heat capacity at constant pressure $c_w$. Let the vessel and immersed parts start at $T_w$ and have combined heat capacity $C_{\mathrm{cal}}$, excluding that water. Assume a common final temperature $T_f$, approximately constant pressure and heat capacities, no phase transition, no chemical reaction and negligible external nonexpansion work. For signed outward heat loss $Q_{\mathrm{loss},\mathrm{out}}$, the combined enthalpy balance isHenceThe loss is positive if the room receives net heat, negative if the room supplies it. If the vessel starts at a different temperature $T_{\mathrm{cal},i}$, replace its warming term by $C_{\mathrm{cal}}(T_f-T_{\mathrm{cal},i})$; do not assume the vessel shared the water's initial temperature. For variable material properties, replace each $mc\Delta T$ by the corresponding integral $m\int c_p(T)dT$ and each vessel term by $\int C_{\mathrm{cal}}(T)dT$. The inferred constant $c_x$ then represents an average over the sample's cooling interval.^[ref]

For a synthetic no-loss example, mix $0.100\mathrm{kg}$ of hot water at $80{}^{\circ }\mathrm{C}$ with $0.200\mathrm{kg}$ of cold water at $20{}^{\circ }\mathrm{C}$ in a vessel initially at $20{}^{\circ }\mathrm{C}$. Stipulate $c_w=4180\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$ and $C_{\mathrm{cal}}=100\mathrm{J}{\mathrm{K}}^{-1}$. The enthalpy balance givesThe hot water releases $17.337\mathrm{kJ}$: the cold water receives $15.485\mathrm{kJ}$ and the vessel $1.852\mathrm{kJ}$. Omitting the vessel predicts $40{}^{\circ }\mathrm{C}$, despite perfect insulation. These are computed numbers from stipulated properties, not laboratory observations.

For an unknown-sample example using the same cold water and vessel, stipulate $m_x=0.100\mathrm{kg}$, $T_x=80{}^{\circ }\mathrm{C}$ and $c_x=450\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$. With no loss, $T_f\approx 22.752{}^{\circ }\mathrm{C}$. Inverting the full balance returns $450\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$; ignoring vessel storage returns about $402\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$. With a positive outward loss, ignoring that loss also biases the inferred $c_x$ downward under these hot-sample conditions. A small water temperature rise makes sensor offsets and loss estimates relatively influential; propagation of uncertainty must include the measured temperatures, masses and calibrated vessel term.

A calorimeter infers transferred heat from a measured change, such as a temperature change and a calibrated heat capacity. The heat-engine calorimetry example requires accounting for the vessel and heat transfer to the surroundings as well as the water.

A practical receiver has an inner vessel, insulation or an outer shield, a lid, a thermometer and a stirrer. Its participating heat capacity includes the immersed parts that follow the water's temperature. Insulation reduces heat transfer to the room; stirring makes a single reading more representative of the contents. These serve different purposes: a well-insulated vessel can still have substantial heat capacity, and a uniform temperature does not imply zero external heat transfer.

The University of Toronto's Heat Capacity (University of Toronto laboratory handout) describes a copper inner vessel, outer shield, thermometer and heated metal block. Weigh the block and receiving water, heat the block in a bath, then transfer it quickly into enough water to cover it. The observed temperature rises, reaches a maximum, then falls. The inferred specific heat capacity comes from the block's cooling and the warming of both water and vessel. In its cooling exercise the handout deliberately exposes the inner vessel to room air, recommends readings every $15\mathrm{s}$, and uses the later common cooling to estimate the earlier loss. Starting below room temperature reduces exchange without guaranteeing cancellation. The handout notes limited time and thermometry for small corrections; it supplies no dataset.^[ref]

For a proposed modern version, independently perform thermometer calibration and calorimeter calibration, record bath and room temperatures, and keep immersion depth, lid position and stirring rate fixed. Ensure the block actually reaches bath temperature; minimize and account for adhering hot bath water. Compare repeated transfers with different delays and a reference sample of known specific heat capacity. A resting run tests environmental heat transfer, while a stirred run with no added sample checks mechanical input. These are proposed controls, not claimed observations from the handout. Sensor delay, changing heat capacity, incomplete thermal equilibrium and material escaping the boundary limit the resulting estimate.

A calorimeter that infers transferred heat from ice melting at a specified equilibrium temperature. The latent heat sets the proportionality after correcting for other thermal changes and extraneous melting.

Calorimeter calibration establishes the response of the actual measurement assembly to a known energy input. It determines a participating heat capacity, not just the empty vessel's mass. For an electrical calibration with an immersed resistor, measure voltage $V(t)$ across that resistor and electric current $I(t)$ through it. If that electrical work is deposited inside the chosen boundary, its input isFor a covered receiver at constant pressure, $C_{\mathrm{eff}}$ describes enthalpy storage; for a rigid fixed-volume assembly, use the matching heat capacity at constant volume. Negligible endpoint mechanical storage and no escaping material are assumed. Thus $E_{\mathrm{el}}/(T_1-T_0)$ overestimates $C_{\mathrm{eff}}$ if outward loss is ignored. Account for lead losses outside the boundary and maintain the same water charge and immersed hardware in calibration and sample runs.

An alternative calibration mixes known hot and cold water portions. With the vessel initially at the cold portion's temperature $T_c$, the mixing calorimetry balance givesThe previous synthetic water example returns $100\mathrm{J}{\mathrm{K}}^{-1}$. The sign matters: attributing room losses to the vessel makes this estimate too large. With both $C_{\mathrm{cal}}$ and the loss unknown, one final temperature supplies only one equation; separate cooling information or controlled independent runs are needed.

A calorimeter heat-loss correction can make the electrical balance quantitative. For a second synthetic example, stipulate $0.100\mathrm{kg}$ of water with $c_w=4180\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$ and immersed hardware with $C_{\mathrm{cal}}=82\mathrm{J}{\mathrm{K}}^{-1}$, so $C_{\mathrm{eff}}=500\mathrm{J}{\mathrm{K}}^{-1}$. Supply $10\mathrm{W}$ for $300\mathrm{s}$, starting at a room temperature of $20{}^{\circ }\mathrm{C}$, with loss coefficient $G=1\mathrm{W}{\mathrm{K}}^{-1}$. The model below gives $T_1\approx 24.512{}^{\circ }\mathrm{C}$, storage $2255.942\mathrm{J}$ and outward loss $744.058\mathrm{J}$. The uncorrected ratio gives about $665\mathrm{J}{\mathrm{K}}^{-1}$; subtracting the loss recovers $500\mathrm{J}{\mathrm{K}}^{-1}$.

A calorimeter heat-loss correction estimates the signed heat exchanged with the room during the measurement. Under Newton's law of cooling, a constant room temperature $T_a$ and a single representative assembly temperature $T$ give the modelHere $P(t)$ is deposited input power, and $G$ is the apparatus loss coefficient in $\mathrm{W}{\mathrm{K}}^{-1}$. After input ceases, the temperature excess shows exponential decay with time constant $\tau =C_{\mathrm{eff}}/G$:A cooling trace determines the ratio $G/C_{\mathrm{eff}}$, not the two factors separately. Combining the cooling trace with a known electrical energy input supplies the missing information. For constant input $P_0$, starting at $T_a$, the heating solution is $T(t)-T_a=(P_0/G)(1-e^{-t/\tau })$; these solutions generate the calibration figure.

For mixing calorimetry, infer cooling behavior only after the sample, water and vessel approach a common temperature. Applying a single-body cooling model while the sample remains much hotter than the water can misestimate the earlier loss. The Toronto handout's area correction assumes the same loss mechanism represents both the mixing interval and subsequent cooling.^[ref] A backward extrapolation to the transfer time is therefore a model-dependent estimate, not the ultimate equilibrium with the room. Extend the model or report a limitation if sensor delay, substantial temperature gradients, changing room temperature, or escaping material invalidate that assumption. In particular, the relevant $C_{\mathrm{eff}}$ after adding a sample includes its heat capacity; an empty-receiver cooling rate need not apply to the loaded receiver.