This MCQ module is based on: Thermodynamic Terms
Thermodynamic Terms
This assessment will be based on: Thermodynamic Terms
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Thermodynamic Terms, System and Surroundings
5.1 Thermodynamics — An Introduction
Chemical reactions are accompanied by energy changes. Some release heat (a candle burning), some absorb heat (ice melting), some release light, and some store chemical energy. Thermodynamics is the branch of science that deals with the energetics of physical and chemical processes. It tells us:
- How much energy is exchanged when a reaction occurs (1st law)
- Whether the reaction will occur spontaneously (2nd law)
- How efficient the energy conversion is
5.2 The System and the Surroundings
To study energy changes, we divide the universe into two parts:
Surroundings: Everything outside the system that can exchange energy or matter with it.
Universe = System + Surroundings.
For example, when we study a chemical reaction in a beaker, the contents of the beaker form the system, and the beaker, air, table, room — all are surroundings.
5.2.1 Types of Systems
Based on the nature of the boundary, systems are classified into three types:
| Type | Exchange of matter | Exchange of energy | Example |
|---|---|---|---|
| Open | Yes | Yes | Boiling water in an open pan |
| Closed | No | Yes | Water in a sealed metal flask |
| Isolated | No | No | Hot tea in a perfect thermos flask (idealised) |
5.3 The State of the System & State Functions
The state of a system is described by giving the values of measurable properties called state variables: pressure (P), volume (V), temperature (T), amount (n), composition.
Path functions: Quantities whose values depend on the route taken — e.g., heat (q) and work (w).
Mountaineering analogy: your altitude at the summit is a state property — same regardless of which trail you took. But the distance walked depends on the route. Altitude ≡ state function; distance walked ≡ path function.
5.4 The Internal Energy (U)
Every substance possesses internal energy U — the sum of all kinetic and potential energies of its constituent molecules: translational, rotational, vibrational, electronic, nuclear and intermolecular interactions.
Internal energy can change by two distinct routes:
- By exchange of heat (q) — energy transfer due to a temperature difference
- By exchange of work (w) — energy transfer through any other mechanism (e.g., pushing a piston, electrical work)
5.4.1 Sign Conventions (IUPAC)
| Quantity | Positive (+) | Negative (−) |
|---|---|---|
| Heat q | Absorbed BY the system (endothermic) | Released BY the system (exothermic) |
| Work w | Work done ON the system (compression) | Work done BY the system (expansion) |
| ΔU | Energy increases | Energy decreases |
5.5 Thermodynamic Processes
A process is the way a system changes from one state to another. Five common types:
| Process | What is constant | Mathematical condition | Example |
|---|---|---|---|
| Isothermal | Temperature (T) | ΔT = 0 | Slow expansion of gas in contact with a thermostat |
| Adiabatic | No heat exchange | q = 0 | Air rushing out of a punctured tyre (rapid) |
| Isobaric | Pressure (P) | ΔP = 0 | Open-vessel reactions (atmospheric pressure) |
| Isochoric | Volume (V) | ΔV = 0 | Reaction in a sealed bomb calorimeter |
| Cyclic | Returns to initial state | ΔU = 0 for one cycle | Refrigerator, heat-engine cycle |
5.5.1 Reversible vs Irreversible Processes
A reversible process proceeds infinitesimally slowly, with the system always in equilibrium with the surroundings. An irreversible process proceeds at finite speed and the system passes through non-equilibrium states (e.g., gas suddenly expanding into vacuum).
🎯 Interactive: Identify the System Type
Pick a real-world example. The simulator tells you whether it is open, closed or isolated, and whether matter and/or energy can cross the boundary.
Type: Open
Matter exchange: Yes | Energy exchange: Yes
Steam (matter) escapes; heat from flame enters and rises into air.
Setup: 1 mole of an ideal gas expands from (P₁=2 atm, V₁=10 L) to (P₂=1 atm, V₂=20 L). It does so by two paths:
Path A: Free expansion into vacuum (irreversible, no external pressure)
Path B: Reversible isothermal expansion at T = 244 K
Path A: P_ext = 0 → w = −P_ext·ΔV = 0 (no work done)
Path B: w_rev = −nRT ln(V₂/V₁) = −(1)(8.314)(244)(ln 2) = −1406 J ≈ −1.4 kJ
ΔU is the same in both paths (state function!) — for isothermal ideal gas, ΔU = 0. So q must adjust: q_A = 0, q_B = +1406 J.
Lesson: Heat and work are path functions; their values depend on the route. Internal energy ΔU is a state function and is route-independent.
Worked Example 5.1: Sign Conventions
A system absorbs 200 J of heat and does 80 J of work on the surroundings. Calculate ΔU.
Heat absorbed BY system: q = +200 J
Work done BY system (energy lost): w = −80 J
ΔU = q + w = 200 + (−80) = +120 J
The system's internal energy rose by 120 J.
Worked Example 5.2: Identify the Process
A gas in a sealed steel cylinder is heated. Identify the type of process and which thermodynamic variables are zero.
ΔV = 0 → w = −P_ext·ΔV = 0.
By 1st law: ΔU = q + w = q (all the heat goes into raising U; none is lost as work). This is why bomb calorimeters measure q_v = ΔU directly.
🎯 Competency-Based Questions
Q1. Which of the following is NOT a state function? L1 Remember
Q2. A pressure cooker on a stove with the safety valve closed exemplifies which type of system? L2 Understand
Q3. State whether True or False: "ΔU depends on the path taken between initial and final states." L2 Understand
Q4. Predict the type of process: a balloon being slowly compressed inside a thermally insulated room. L3 Apply
Q5. HOT: Two identical gases are taken from state A to state B by two different paths. Path 1 is reversible and does 200 J of work; Path 2 is irreversible and does 150 J of work. Compare ΔU and the heat absorbed in each. L5 Evaluate
Path 1: w₁ = −200 J → q₁ = X − w₁ = X + 200 J.
Path 2: w₂ = −150 J → q₂ = X + 150 J.
So q₁ > q₂: the reversible path absorbs MORE heat. This is consistent with the principle that reversible processes give maximum work and absorb maximum heat for the same ΔU.
🧠 Assertion–Reason Questions
Choose: (A) Both true, R explains A. (B) Both true, R doesn't explain A. (C) A true, R false. (D) A false, R true.
A: Internal energy is a state function.
R: The change in internal energy depends only on the initial and final states of a system.
A: Heat absorbed by a system is given a positive sign.
R: Heat raises the internal energy of the system, which is a positive change.
A: A perfectly isolated system can exchange neither matter nor energy with the surroundings.
R: Isolated systems exist abundantly in nature.
Frequently Asked Questions — Thermodynamic Terms, System and Surroundings
What is a thermodynamic system?
What is the difference between open, closed and isolated systems?
What is a state function in thermodynamics?
What are intensive and extensive properties?
What is thermodynamic equilibrium?
Why is the universe considered an isolated system?
🎯 Practise Chemistry
Sit a full paper on what you have been studying, marked question by question.