2 The Laws of Thermodynamics
“The law that entropy always increases holds, I think, the supreme position among the laws of Nature. If someone points out to you that your pet theory of the universe is in disagreement with Maxwell’s equations, then so much the worse for Maxwell’s equations. But if your theory is found to be against the second law of thermodynamics I can give you no hope; there is nothing for it but to collapse in deepest humiliation.” – Arthur Eddington
The laws of thermodynamics are not suggestions. They are not policies that can be changed. They are not technological barriers that can be overcome with sufficient cleverness. They are the fundamental constraints on every energy conversion process in the universe.
Every energy technology (from a campfire to a nuclear reactor, from a solar panel to a hydrogen fuel cell) is a conversion device. It transforms energy from one form to another. The laws of thermodynamics govern what conversions are possible and set hard limits on how efficiently they can be performed.
Understanding these laws is not optional for energy literacy. They are the “Principle” foundation of our Framework for Change, the bedrock upon which all Technology, Product, Policy, and Outcome rest.
2.1 The Zeroth Law: Temperature and Equilibrium
The Zeroth Law was formalized last (in the 1930s) but is logically prior to the others:
If system A is in thermal equilibrium with system C, and system B is also in thermal equilibrium with system C, then A and B are in thermal equilibrium with each other.
This seemingly trivial statement establishes that temperature is a meaningful quantity, something that two objects in thermal equilibrium share. It is why thermometers work: the thermometer reaches equilibrium with your body, and the reading tells you something about your temperature.
For energy systems, the Zeroth Law means:
- Heat flows from hot to cold until equilibrium is reached
- Differences in temperature represent exploitable potential
- When temperatures equalize, no more work can be extracted
A hot reservoir and cold reservoir at different temperatures constitute an opportunity. When they reach equilibrium, that opportunity is exhausted.
2.2 The First Law: Conservation of Energy
The First Law is the principle of energy conservation:
Energy cannot be created or destroyed; it can only be transformed from one form to another. The total energy of an isolated system remains constant.
Mathematically, for a closed system:
\[ \Delta U = Q - W \]
Where:
- \(\Delta U\) = change in internal energy of the system
- \(Q\) = heat added to the system
- \(W\) = work done by the system
This can be rewritten in differential form:
\[ dU = \delta Q - \delta W \]
2.2.1 Energy as Absolute Currency
Unlike money, which governments can print at will, energy obeys strict conservation. Vaclav Smil calls energy “the only universal currency”: you cannot counterfeit it, you cannot create it from nothing, and every transaction must balance.
The First Law has profound implications for energy systems:
1. No free energy. You cannot get energy from nothing. Perpetual motion machines of the first kind (devices that produce work without any energy input) are impossible. Every scam that promises “free energy” violates this law.
2. All energy is accounted for. In any energy conversion, input equals output (plus any stored change). If a power plant consumes 1,000 MW of chemical energy (fuel), that energy goes somewhere: some becomes electricity, some becomes waste heat, but the total is conserved.
3. Efficiency has rigorous meaning. We define First Law efficiency as: \[ \eta_{I} = \frac{\text{Useful output energy}}{\text{Input energy}} \]
For any real process, \(\eta_{I} \leq 1\) (or ≤ 100%). This isn’t a practical limit; it’s absolute.
2.2.2 Forms of Energy
Energy exists in multiple interconvertible forms:
Kinetic energy: Energy of motion \[ E_k = \frac{1}{2}mv^2 \] A 1,500 kg car at 30 m/s (67 mph) has kinetic energy: \[ E_k = \frac{1}{2}(1500)(30)^2 = 675,000 \text{ J} = 0.19 \text{ kWh} \]
Gravitational potential energy: Energy of height \[ E_p = mgh \] Water in a reservoir 100 m above a turbine has 0.27 Wh/kg of gravitational potential, tiny compared to chemical fuels but accessible and reversible.
Chemical energy: Energy stored in molecular bonds. Combustion releases this energy: \[ \text{CH}_4 + 2\text{O}_2 \rightarrow \text{CO}_2 + 2\text{H}_2\text{O} + 890 \text{ kJ/mol} \] The 890 kJ was stored in the methane’s C-H bonds.
Electrical energy: Energy of charge separation and flow \[ E = qV \quad \text{and} \quad P = IV \]
Electromagnetic (radiant) energy: Energy of photons \[ E_{photon} = hf = \frac{hc}{\lambda} \] A photon of red light (700 nm) carries 1.77 eV; blue light (450 nm) carries 2.76 eV.
Nuclear energy: Energy of nuclear binding \[ E = \Delta m \cdot c^2 \] When uranium-235 fissions, about 0.09% of its mass converts to energy, releasing 200 MeV per fission event.
Thermal energy: Energy of molecular motion. The internal energy of a substance depends on temperature and molecular structure.
2.2.3 The First Law in Practice
Consider a combined-cycle natural gas power plant:
Inputs: - Natural gas: 1,000 MW thermal (chemical energy in methane) - Air (contains oxygen for combustion)
Outputs: - Electricity: 600 MW - Waste heat in exhaust: 250 MW - Waste heat in cooling water: 150 MW
First Law check: 600 + 250 + 150 = 1,000 MW ✓
The First Law is satisfied: all energy is accounted for. But notice that only 60% became electricity. The remaining 40% became waste heat. This isn’t a failure of engineering; it’s a consequence of the Second Law.
2.2.4 Enthalpy and Heating Values
For chemical reactions at constant pressure (typical for combustion), we use enthalpy (\(H\)): \[ H = U + PV \]
The change in enthalpy equals heat transferred at constant pressure: \[ \Delta H = Q_p \]
For fuels, we define heating values:
Higher Heating Value (HHV): Total heat released when fuel burns and all products are cooled to 25°C, including condensation of water vapor.
Lower Heating Value (LHV): Heat released excluding the latent heat of water vapor (water exits as gas).
| Fuel | HHV (MJ/kg) | LHV (MJ/kg) | HHV (kWh/kg) |
|---|---|---|---|
| Hydrogen | 142 | 120 | 39.4 |
| Natural gas | 55 | 50 | 15.3 |
| Gasoline | 46 | 44 | 12.8 |
| Diesel | 45 | 43 | 12.5 |
| Coal (bituminous) | 32 | 31 | 8.9 |
| Wood (dry) | 20 | 18 | 5.6 |
| Ethanol | 30 | 27 | 8.3 |
The difference between HHV and LHV matters significantly for hydrogen (15% difference) and less for coal (~3%). Power plant efficiency calculations depend on which heating value is used, a common source of confusion when comparing reported efficiencies across different sources.
2.3 The Second Law: Entropy and Irreversibility
The First Law tells us energy is conserved. The Second Law tells us something more profound: not all energy is equally useful. There is a directionality to natural processes.
There are several equivalent formulations:
Clausius statement: Heat cannot spontaneously flow from a colder body to a hotter body.
Kelvin-Planck statement: It is impossible to construct a heat engine that, operating in a cycle, produces no effect other than extracting heat from a single reservoir and performing an equivalent amount of work.
Entropy statement: The total entropy of an isolated system never decreases. For any spontaneous process: \[ \Delta S_{total} \geq 0 \]
2.3.1 Understanding Entropy
Entropy (\(S\)) is perhaps the most misunderstood concept in physics. It is often described as “disorder,” but this is imprecise and sometimes misleading.
More rigorously, entropy measures the dispersal of energy, or equivalently, the number of microscopic configurations (microstates) consistent with a macroscopic state: \[ S = k_B \ln \Omega \]
Where \(k_B\) is Boltzmann’s constant and \(\Omega\) is the number of microstates.
For a reversible heat transfer at temperature \(T\): \[ dS = \frac{\delta Q_{rev}}{T} \]
Key properties of entropy: - Entropy is a state function (depends only on current state, not history) - Entropy increases in all spontaneous processes - Entropy can decrease locally only if it increases more elsewhere - Maximum entropy corresponds to equilibrium, meaning no more work can be extracted
The Second Law’s deepest meaning: natural processes tend toward states of greater entropy, meaning greater dispersal of energy and greater probability in the statistical mechanical sense. A hot object cooling in a cold room is overwhelmingly more probable than a cold room spontaneously transferring heat to make a hot object hotter.
2.3.2 Energy Quality: Why the Second Law Matters
The Second Law explains a crucial asymmetry: energy forms differ in “quality” or usefulness.
High-quality (low-entropy) energy can do many things: - Electricity can power motors, computers, lights, heaters - High-temperature heat can generate electricity or drive industrial processes - Mechanical motion can be converted to electricity efficiently
Low-quality (high-entropy) energy can do few things: - Room-temperature heat can barely do anything useful - Dispersed waste heat cannot be recovered economically
This quality gradient drives the direction of all energy conversions:
| From | To | Ease |
|---|---|---|
| Mechanical → Electrical | ≈95% efficient | Easy |
| Electrical → Mechanical | ≈95% efficient | Easy |
| Chemical → Thermal | ≈100% possible | Easy |
| Electrical → Thermal | ≈100% possible | Easy |
| Thermal → Mechanical | ≤ Carnot limit | Hard |
| Thermal → Electrical | ≤ Carnot limit | Hard |
| Low-temp thermal → High-temp thermal | Requires work input | Hard |
Every heat engine (coal plant, gas turbine, nuclear reactor, car engine) struggles against this thermodynamic asymmetry. They can never convert heat to work with 100% efficiency because some heat must be rejected to satisfy the Second Law.
2.4 Carnot Efficiency: The Best You Can Do
Sadi Carnot, a French military engineer, published his analysis of heat engine efficiency in 1824 in Réflexions sur la puissance motrice du feu (Reflections on the Motive Power of Fire). His work established that the most efficient possible heat engine operates between two thermal reservoirs in a reversible cycle.
The Carnot efficiency sets an absolute upper bound:
\[ \eta_{Carnot} = 1 - \frac{T_C}{T_H} \]
Where: - \(T_H\) = absolute temperature of the hot reservoir (Kelvin) - \(T_C\) = absolute temperature of the cold reservoir (Kelvin)
Carnot efficiency requires temperatures in Kelvin (K) or Rankine (R), not Celsius or Fahrenheit.
To convert: \(T_K = T_C + 273.15\)
Using Celsius or Fahrenheit gives meaningless results. A steam plant at 500°C and 30°C does NOT have efficiency \(1 - 30/500 = 94\%\). The correct calculation uses 773 K and 303 K: \(1 - 303/773 = 60.8\%\).
2.4.1 Carnot Calculations for Real Systems
Subcritical coal-fired power plant: - Steam temperature: 540°C = 813 K - Cooling water temperature: 30°C = 303 K
\[ \eta_{Carnot} = 1 - \frac{303}{813} = 0.627 = 62.7\% \]
Best real subcritical coal plants achieve ~38% efficiency, about 60% of Carnot.
Supercritical coal plant: - Steam temperature: 600°C = 873 K - Cooling water: 30°C = 303 K
\[ \eta_{Carnot} = 1 - \frac{303}{873} = 0.653 = 65.3\% \]
Best supercritical plants achieve ~45%, about 69% of Carnot.
Combined cycle gas turbine (CCGT): - Combustion temperature: 1,400°C = 1,673 K - Stack exhaust: 100°C = 373 K (before heat recovery) - Final rejection: 35°C = 308 K
The CCGT’s genius is two-stage operation. The gas turbine operates between very high temperature and intermediate temperature; the steam cycle captures remaining heat.
Overall Carnot limit using extreme temperatures: \[ \eta_{Carnot} = 1 - \frac{308}{1673} = 0.816 = 81.6\% \]
Best CCGTs achieve ~64% efficiency, about 78% of theoretical maximum.
Conventional geothermal plant: - Hydrothermal fluid: 180°C = 453 K - Cooling: 25°C = 298 K
\[ \eta_{Carnot} = 1 - \frac{298}{453} = 0.342 = 34.2\% \]
Real geothermal plants achieve 10-20% efficiency. This thermodynamic penalty explains why geothermal, despite “free” fuel, often struggles economically against gas plants.
Superhot rock geothermal (future technology): - Rock temperature: 400°C = 673 K - Cooling: 25°C = 298 K
\[ \eta_{Carnot} = 1 - \frac{298}{673} = 0.557 = 55.7\% \]
The promise of superhot rock geothermal: higher temperatures dramatically improve conversion efficiency, potentially making geothermal cost-competitive everywhere.
2.4.2 The Carnot Lessons
1. Higher hot-side temperatures enable higher efficiency. This is why engineers pursue ever-higher combustion temperatures, supercritical steam, and advanced materials that can withstand extreme heat.
2. The cold side matters too. A power plant in Phoenix (cooling water at 40°C) is inherently less efficient than one in Maine (cooling water at 15°C). This isn’t engineering failure; it’s physics.
3. The gap between real and Carnot efficiency represents irreversibilities. Every friction loss, every heat transfer across a finite temperature difference, every pressure drop generates entropy and reduces efficiency.
4. Some resources can never be converted efficiently. Ocean thermal energy conversion (OTEC), using the ~20°C temperature difference between tropical surface water and deep water, has a Carnot limit of only ~7%, and real systems achieve far less.
Why are gasoline car engines only ~20-25% efficient?
Peak combustion temperature: ~2,500 K Effective average: ~1,000 K (combustion is brief) Exhaust temperature: ~800 K Cooling system rejects heat at: ~370 K
Using effective temperatures: \[ \eta_{Carnot} \approx 1 - \frac{370}{1000} = 63\% \]
The gap from 63% to actual 25% comes from: - Heat loss through cylinder walls (~15%) - Friction in pistons, bearings (~5%) - Incomplete combustion (~3%) - Pumping losses from throttling (~10%) - Part-load operation (engines rarely run at peak efficiency)
No amount of automotive engineering will achieve 63%. But note: electric motors are 85-95% efficient because they bypass the heat engine pathway entirely.
2.5 Heat Pumps: Turning the Carnot Equation Around
Heat pumps appear to perform magic: they can deliver more heat energy than the electrical energy they consume. But this violates neither the First nor Second Law; it cleverly exploits thermodynamics.
A heat pump moves heat from a cold reservoir to a hot reservoir, requiring work input:
\[ Q_H = W + Q_C \]
Where: - \(Q_H\) = heat delivered to the hot side (your house) - \(W\) = work input (electricity consumed) - \(Q_C\) = heat extracted from the cold side (outside air, ground, water)
The Coefficient of Performance (COP) for heating measures output heat per unit work input: \[ COP_{heating} = \frac{Q_H}{W} = \frac{Q_H}{Q_H - Q_C} \]
For an ideal (Carnot) heat pump operating between temperatures \(T_H\) and \(T_C\): \[ COP_{Carnot} = \frac{T_H}{T_H - T_C} \]
2.5.1 Heat Pump Calculations
Ground-source heat pump: - Ground temperature (cold source): 10°C = 283 K - Indoor temperature (hot sink): 21°C = 294 K
\[ COP_{Carnot} = \frac{294}{294 - 283} = \frac{294}{11} = 26.7 \]
Real ground-source heat pumps achieve COP of 3.5-5.0, far below ideal but still remarkable. For every 1 kWh of electricity, you get 3.5-5 kWh of heating.
Air-source heat pump on a cold day: - Outdoor temperature: -10°C = 263 K - Indoor temperature: 21°C = 294 K
\[ COP_{Carnot} = \frac{294}{294 - 263} = \frac{294}{31} = 9.5 \]
Real air-source heat pumps achieve COP of 2-3 at these temperatures. Performance degrades as outdoor temperature drops because the temperature difference increases.
Air-source heat pump on a mild day: - Outdoor temperature: 10°C = 283 K - Indoor temperature: 21°C = 294 K
\[ COP_{Carnot} = \frac{294}{294 - 283} = \frac{294}{11} = 26.7 \]
Real COP might be 4-5 under these favorable conditions.
2.5.2 Why Heat Pumps Matter for Decarbonization
Heat pumps are central to climate strategy because:
1. They multiply clean electricity. A COP of 3 means 1 kWh of clean electricity delivers 3 kWh of heating, equivalent to 300% efficiency in First Law terms.
2. They outperform direct resistance heating. Electric baseboard heaters have COP = 1 exactly (by the First Law). Heat pumps are 2-5× better.
3. They often beat gas furnaces on primary energy. A 95%-efficient gas furnace delivers 0.95 kWh of heat per kWh of gas. If electricity comes from a 50%-efficient gas plant, a heat pump with COP of 3 delivers 1.5 kWh of heat per kWh of gas consumed at the plant, 58% better than burning gas directly.
4. They work in reverse as air conditioners. The same equipment cools in summer and heats in winter, improving economics.
5. They enable beneficial electrification. Switching heating from gas to electricity is essential for decarbonization, but only makes sense if electricity is used efficiently.
Heat pumps exemplify the Principle → Technology → Product → Policy → Outcome chain:
Principle: Second Law permits moving heat from cold to hot with work input; Carnot COP sets limits.
Technology: Vapor-compression cycle using refrigerants (R-410A, R-32, CO2); variable-speed compressors; optimized heat exchangers.
Product: Mitsubishi Hyper-Heating (works to -13°F), Carrier Infinity (COP 4.2 at 47°F), Daikin Fit.
Policy: IRA tax credits (up to $2,000 for heat pumps), state incentives, building code requirements for “heat pump ready” construction.
Outcome: U.S. heat pump sales exceeded gas furnace sales in 2022 for the first time (Air-Conditioning, Heating, and Refrigeration Institute), marking the beginning of heating electrification.
2.6 The Energy Density Hierarchy
Different energy storage mechanisms hold vastly different amounts of energy per unit mass. This hierarchy has profound implications for which energy carriers suit which applications.
2.6.1 The Hierarchy Quantified
| Storage Type | Example | Energy Density (Wh/kg) | Ratio to Li-ion |
|---|---|---|---|
| Gravitational | Water raised 100m | 0.27 | 0.001× |
| Mechanical (flywheel) | Carbon fiber at max speed | 30-50 | 0.15× |
| Lead-acid battery | Car starter battery | 30-50 | 0.15× |
| Lithium-ion battery | EV battery pack | 150-300 | 1× |
| Hydrogen (compressed) | 700 bar tank | 1,200 (system) | 5× |
| Hydrogen (liquefied) | Cryogenic tank | 2,000 (system) | 8× |
| Ethanol | Biofuel | 7,500 | 30× |
| Gasoline | Petroleum fuel | 12,000 | 48× |
| Diesel/Jet fuel | Aviation, trucks | 12,500 | 50× |
| Natural gas (LNG) | Liquefied | 14,000 | 56× |
| Uranium-235 (fission) | Nuclear fuel | 24,000,000 | 96,000× |
The range spans eight orders of magnitude, from 0.27 Wh/kg for pumped hydro to 24,000,000 Wh/kg for uranium fission.
2.6.2 Implications of the Hierarchy
1. Transportation mode depends on energy density requirements.
Short-range, stop-and-go (urban delivery, commuting): Batteries work well despite lower density because regenerative braking recovers energy and daily range requirements are modest.
Long-range, continuous power (trucking, shipping, aviation): Energy density becomes critical. A battery with energy equivalent to a transatlantic flight’s jet fuel would weigh more than the aircraft.
2. Batteries will never match liquid fuels on density.
Lithium-ion batteries at ~250 Wh/kg are approaching theoretical limits for their chemistry. Solid-state batteries might reach 400-500 Wh/kg. Gasoline is at 12,000 Wh/kg. The gap will never close through battery improvements alone.
3. This explains persistent use of fossil fuels in “hard to electrify” sectors.
Aviation, long-haul trucking, and shipping need high energy density. Until alternative liquid fuels (synthetic or bio-based) or hydrogen infrastructure mature, these sectors will remain dependent on petroleum-derived fuels.
4. Nuclear’s density explains its unique characteristics.
A single uranium fuel pellet (6 grams) contains as much energy as: - 17,000 cubic feet of natural gas - 1,780 pounds of coal - 149 gallons of oil
This extreme density means nuclear plants require vanishingly small fuel volumes, enabling 18-24 month refueling cycles and minimal transportation infrastructure. It also means the waste is extraordinarily concentrated, both a virtue (small volume) and a challenge (intense radioactivity).
2.6.3 Power Density vs. Energy Density
Power density (rate of energy delivery per unit mass) often trades off against energy density (total energy per unit mass):
| Technology | Energy Density | Power Density | Character |
|---|---|---|---|
| Supercapacitor | Low (5-15 Wh/kg) | Very high (10,000 W/kg) | Bursts |
| Li-ion battery | Medium (150-300 Wh/kg) | Medium (200-2000 W/kg) | Balanced |
| Fuel cell | High (1000+ Wh/kg system) | Low (50-200 W/kg) | Marathon |
| Gasoline + ICE | Very high (12,000 Wh/kg fuel) | Medium (engine ~1000 W/kg) | Versatile |
This tradeoff appears throughout energy systems: - EVs need both high energy density (range) and high power density (acceleration) - Grid storage needs energy density (duration) but power density varies by application - Hybrid vehicles combine battery (power) with fuel (energy)
A Boeing 787-9 on a New York to London flight: - Distance: 5,500 km - Fuel consumption: ~5.5 tonnes per 1,000 km - Total fuel: ~30,000 kg - Fuel energy: 30,000 kg × 12 kWh/kg = 360,000 kWh = 360 MWh
To carry this energy in lithium-ion batteries (250 Wh/kg): \[ \text{Battery mass} = \frac{360,000,000 \text{ Wh}}{250 \text{ Wh/kg}} = 1,440,000 \text{ kg} \]
The aircraft’s maximum takeoff weight is 254,000 kg total. The battery alone would be 5.7× the entire aircraft’s maximum weight.
Even with hypothetical future batteries at 500 Wh/kg: 720,000 kg, still 2.8× the aircraft.
Even at an impossible 2,000 Wh/kg: 180,000 kg, which is 70% of max takeoff weight, leaving almost nothing for structure, passengers, or cargo.
Conclusion: Long-haul aviation will require liquid fuels (sustainable aviation fuel or synthetic fuels) or potentially hydrogen (with major aircraft redesign). Batteries are thermodynamically excluded for this application.
2.7 Dimensional Analysis for Energy
Dimensional analysis is a powerful tool for checking calculations and developing intuition. Every energy-related equation must be dimensionally consistent.
2.7.1 Fundamental Dimensions
Energy has dimensions of: \[ [E] = ML^2T^{-2} \]
Where M = mass, L = length, T = time.
In SI units: \(1 \text{ J} = 1 \text{ kg} \cdot \text{m}^2 \cdot \text{s}^{-2}\)
Power has dimensions of energy per time: \[ [P] = ML^2T^{-3} \]
In SI units: \(1 \text{ W} = 1 \text{ J/s} = 1 \text{ kg} \cdot \text{m}^2 \cdot \text{s}^{-3}\)
2.7.2 Checking Equations
The discipline of dimensional analysis catches errors before they propagate:
Kinetic energy: \(E = \frac{1}{2}mv^2\) \[ [E] = M \cdot (LT^{-1})^2 = ML^2T^{-2} \quad \checkmark \]
Gravitational potential: \(E = mgh\) \[ [E] = M \cdot (LT^{-2}) \cdot L = ML^2T^{-2} \quad \checkmark \]
Wind power: \(P = \frac{1}{2}\rho A v^3\) \[ [P] = (ML^{-3}) \cdot L^2 \cdot (LT^{-1})^3 = ML^2T^{-3} \quad \checkmark \]
If someone claims wind power scales as \(v^2\) rather than \(v^3\), dimensional analysis immediately reveals the error because the dimensions wouldn’t work.
2.7.3 Estimating Theoretical Limits
Dimensional analysis can estimate theoretical limits from fundamental constants:
Chemical energy density is bounded by typical bond energies (1-5 eV) and atomic masses: - A C-H bond has energy ~4 eV - A typical hydrocarbon has roughly 2 C-H bonds per carbon - Per CH2 unit (molecular weight 14): \[ \frac{8 \text{ eV} \times 1.6 \times 10^{-19} \text{ J/eV} \times 6 \times 10^{23}}{0.014 \text{ kg}} \approx 5 \times 10^7 \text{ J/kg} \approx 14,000 \text{ Wh/kg} \]
This is within a factor of ~2 of gasoline’s actual value, validating the approach.
Nuclear energy density comes from mass-energy equivalence: - Fission releases ~0.09% of mass as energy - \(E = 0.0009 \times m \times c^2\) - Per kg: \(0.0009 \times (3 \times 10^8)^2 = 8 \times 10^{13}\) J/kg ≈ \(2 \times 10^{10}\) Wh/kg
This matches U-235’s energy density to within an order of magnitude.
2.7.4 Useful Scaling Relations
Wind power scales as velocity cubed: \(P \propto v^3\) - Double wind speed → 8× power - This is why wind farm developers obsess over sites with just a few m/s higher average wind speed
Solar power scales linearly with area: \(P = G \cdot A \cdot \eta\) - Double the panel area → double the power - No clever arrangement changes this
Carnot efficiency improves with temperature difference: \[ \eta = 1 - \frac{T_C}{T_H} = \frac{T_H - T_C}{T_H} \] - Larger temperature difference → higher efficiency - But materials limits constrain \(T_H\)
2.8 Summary
The laws of thermodynamics constrain all energy systems:
Zeroth Law: Temperature is well-defined; systems in thermal equilibrium have equal temperatures; heat flows from hot to cold toward equilibrium.
First Law: Energy is conserved in every process. Input equals output, always. No exceptions. This defines efficiency limits.
Second Law: Not all energy is equally useful. Entropy increases in spontaneous processes. Heat engines have maximum (Carnot) efficiency that depends only on temperatures.
Carnot Efficiency: \(\eta_{max} = 1 - T_C/T_H\) for heat engines; \(COP_{max} = T_H/(T_H - T_C)\) for heat pumps. These are absolute limits, not engineering targets.
Energy Density Hierarchy: Ranges eight orders of magnitude from mechanical to nuclear. This hierarchy explains fuel choices across applications.
Power vs. Energy Density: These trade off against each other; different applications optimize differently.
These laws don’t tell us which energy sources to use; that involves economics, politics, and values. But they tell us what’s possible and what isn’t. Every energy claim should be checked against thermodynamics first. If a proposal violates these laws, no amount of innovation, investment, or policy support will make it work.
The thermodynamic laws are the deepest Principles in our framework. They set absolute boundaries that no technology, product, or policy can transcend. When evaluating any energy proposal, ask:
- Does this respect conservation (First Law)?
- Does the claimed efficiency exceed Carnot limits (Second Law)?
- Is the energy density claim physically plausible?
If a proposal violates these principles, it is not merely difficult; it is impossible.
2.9 Readings
- first_law.txt: First Law of Thermodynamics (conservation, internal energy, enthalpy)
- second_law.txt: Second Law of Thermodynamics (entropy, Carnot cycle, irreversibility)
- SEWTHA technical chapters on efficiency limits
2.10 Exercises
Carnot Calculation: A coal plant operates with steam at 550°C and cooling water at 25°C. A combined cycle gas plant operates with combustion at 1,350°C and cooling at 35°C.
- Calculate the Carnot efficiency for each plant.
- If the coal plant achieves 42% and the CCGT achieves 62%, what fraction of the Carnot limit does each reach?
- Why might the CCGT get closer to its Carnot limit than the coal plant?
Heat Pump Analysis: Consider a ground-source heat pump (ground at 12°C) versus an air-source heat pump (outdoor air at -5°C), both heating a house to 21°C.
- Calculate the Carnot COP for each system.
- If real-world COPs are 4.5 (ground-source) and 2.5 (air-source), how much electricity does each use to deliver 100 kWh of heat?
- If electricity costs $0.15/kWh and natural gas costs $1.20/therm (29.3 kWh), which heating option is cheapest? (Assume 95% efficient gas furnace.)
Why Can’t We Break Even?: A modern supercritical coal plant achieves 45% efficiency despite a Carnot limit of 65%. List and briefly explain four sources of this 20-percentage-point gap. Which losses are reducible by engineering, and which are fundamental?
Energy Density Comparison: Calculate the fuel/battery mass required for a 500 km trip:
- Gasoline car at 8 L/100 km (gasoline density 0.75 kg/L)
- Diesel truck at 25 L/100 km (diesel density 0.85 kg/L)
- Electric car at 18 kWh/100 km with 250 Wh/kg battery
- Hydrogen fuel cell vehicle at 1 kg H2/100 km (compressed at 700 bar, 5% of system mass is H2)
Discuss implications for vehicle design.
Dimensional Check: A colleague claims that battery energy scales as \(E = \sigma A t^2\) where \(\sigma\) is a conductivity-like parameter, \(A\) is electrode area, and \(t\) is time. Check this dimensionally. What should the correct relationship look like?
Second Law Efficiency: A natural gas furnace converts 95% of fuel energy to heat in a house at 20°C when outdoor temperature is -10°C.
- What is the First Law efficiency of the furnace?
- Calculate the exergy (maximum useful work) available from burning 1 kWh of natural gas at 2,000°C flame temperature, rejecting heat at -10°C.
- What is the Second Law (exergetic) efficiency of using this high-quality chemical energy just for low-temperature space heating?
- Compare to a heat pump with COP of 3.0. If electricity is generated from natural gas at 55% efficiency, which system uses primary energy more effectively?
Geothermal Limits: Enhanced geothermal systems might access rock at 200°C (conventional), 350°C (deep EGS), or 450°C (superhot rock).
- Calculate the Carnot efficiency for each, assuming 20°C rejection temperature.
- Why do real geothermal plants typically achieve only 50-60% of Carnot efficiency?
- If a conventional hydrothermal plant costs $3,000/kW and achieves 12% efficiency, estimate what cost per kW a superhot rock plant could reach while maintaining the same cost per kWh, assuming it achieves proportionally higher efficiency.