Chemical Engineering Tutorials: Relationship Between Heat Transfer and the First Law of Thermodynamics

Monday, 9 March 2026

Relationship Between Heat Transfer and the First Law of Thermodynamics

In this topic we are interested in the efficiency of heat engines. We are going to build upon the knowledge of thermodynamics and show how heat transfer plays an integral role in managing and promoting the efficiency of a wide range of energy conversion devices. 

Remember that we have defined a heat engine previously as any device that continuously or cyclically operates and converts heat to work. Power plants and thermoelectric devices are examples of heat engine. 

It is extremely important to improve the efficiency of heat engines. For example, an efficient combustion engine consumes less fuel to produce a given amount of work thus reduces emissions of pollutants. More efficient thermoelectric devices can generate more electricity from waste heat. 

The second law of thermodynamics can be represented in a number of distinct but comparable ways and is frequently employed when efficiency is an issue. The KelvinPlanck statement is very relevant to the operation of a heat engine. It states:

"It is impossible for any system to operate in a thermodynamic cycle and deliver a net amount of work to its surroundings while receiving energy by heat transfer from a single thermal reservoir"

Remember that a thermodynamic cycle is a process for which the initial and final states of the system are identical. Consequently, the energy stored in the system does not change between the initial and final states, and the first law of thermodynamics reduces to W = Q.

Because of the Kelvin–Planck statement, a heat engine must exchange heat with two or more reservoirs, gaining thermal energy from the higher-temperature reservoir and rejecting thermal energy to the lower-temperature reservoir. Therefore, converting all of the input heat to work is impossible and:

W = Qin – Qout,

where Qin and Qout are both defined to be positive. i.e.,

Qin = heat transferred from the high temperature source to the heat engine

Qout = the heat transferred from the heat engine to the low temperature sink.

The efficiency of a heat engine is the fraction of heat transferred into the system that is converted to work:

For a reversible process the ratio Qout/Qin is equal to the ratio of the absolute temperatures of the respective reservoirs (From the 2nd Law of Thermodynamics. Thus, the efficiency of a heat engine undergoing a reversible process, i.e., Carnot efficiency, ηC, (as previously discussed) is given by:

where Tc and Th are the absolute temperatures of the low and high temperature reservoirs, respectively. 

The Carnot efficiency is the maximum possible efficiency that any heat engine can achieve operating between those two temperatures. Any real heat engine, which will necessarily undergo an irreversible process, will have a lower efficiency.

From our knowledge of thermodynamics, we know that, for heat transfer to take place reversibly, it must occur through an infinitesimal temperature difference between the reservoir and heat engine. In heat transfer mechanisms, in order for heat transfer to occur, there must be a nonzero temperature difference between the reservoir and the heat engine. This introduces irreversibility and reduces the efficiency. 

Let us now consider a more realistic heat engine model where heat is transferred into the engine through a thermal resistance Rt,h, while heat is extracted from the engine through a second thermal resistance Rt,c where subscripts h and c refer to the hot and cold sides of the heat engine respectively. 

Let us now consider a more realistic heat engine model where heat is transferred into the engine through a thermal resistance Rt,h, while heat is extracted from the engine through a second thermal resistance Rt,c where subscripts h and c refer to the hot and cold sides of the heat engine respectively. This is shown in the following figure:

 

These thermal resistances are associated with heat transfer between the heat engine and the reservoirs across a nonzero temperature difference through mechanisms of conduction, convection and/or radiation. E.g., the resistances could represent conduction through walls separating the heat engine from the two reservoirs

Note that the reservoir temperatures are still Th and Tc but that the temperatures seen by the heat engine are Th,i < Th and Tc,i > Tc, as shown in the diagram above. The heat engine is still assumed to be internally reversible, and its efficiency is still the Carnot efficiency.

However, the Carnot efficiency is now based on the internal temperatures Th,i and Tc,i . Therefore in order to account for the realistic irreversible process, the efficiency, ηm, is as follows: 

where the ratio Qout/Qin, has been replaced by the corresponding ratio of heat rates, qout/qin. This replacement is based on applying energy conservation at an instant in time. Utilizing the definition of a thermal resistance, the heat transfer rates into and out of the heat engine are given by:

The above equations can be solved for the internal temperatures to result in:

For the Tc,i equation, qout has already been related to qin and ηm, The more realistic, modified efficiency can then be expressed as:

Solving for ηm, results in:

where Rtot = Rt,h + Rt,c.

It is evident that ηm = ηC only if the thermal resistances Rt,h and Rt,c could somehow be made infinitesimally small (or if qin  0). For realistic (nonzero) values of Rtot, ηm < ηC, and ηm further deteriorates as either Rtot or qin increases. As an extreme case, note that ηm = 0 when Th = Tc + qinRtot , meaning that no power could be produced even though the Carnot efficiency is nonzero.

In addition to the efficiency, another important parameter to consider is the power output of the heat engine, given by:















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Relationship Between Heat Transfer and the First Law of Thermodynamics

In this topic we are interested in the efficiency of heat engines. We are going to build upon the knowledge of thermodynamics and show how h...