2.5.16 · D1Thermodynamics (Chemical)

Foundations — Coupling reactions — driving unfavorable reactions

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Before you can trust the parent note's punchline — " adds, multiplies" — you must own every symbol it throws at you. We build them one at a time, from nothing. If a word appears in a later definition, it was defined earlier. No skipping.


0. The characters in the story

The parent note secretly assumes you already know: energy, spontaneity, , , , , , state function, intermediate, equilibrium constant , , , and kJ/mol. We define each below, anchor it to a picture, and say why the topic needs it.


1. Energy going "downhill" vs "uphill"

  • Downhill (favorable): the system loses free energy, so it happens on its own.
  • Uphill (unfavorable): the system would have to gain free energy, so it stalls — unless something else pushes.

Why the topic needs it: the whole idea of "coupling" is tying an uphill ball to a downhill ball so the heavy one drags the light one up. We must first agree on what "up" and "down" mean.


2. The symbol ("delta") — a change, an after-minus-before

Why the topic needs it: every quantity in this chapter — , , — is a change across the reaction, never an absolute amount. The sign of that change is the whole game.


3. — absolute temperature (in kelvin)

Why the topic needs it: is a dial. In Example 1 of the parent, turning the temperature dial up is exactly what makes carbon's reaction "downhill enough" to reduce zinc. Temperature multiplies the entropy term (next), so it controls how strongly entropy pushes.


4. Enthalpy change — the heat drive

Why the topic needs it: releasing heat is one of the two reasons a reaction wants to go. It's one half of the free-energy formula in §6.


5. Entropy change — the "spreading out" drive

Why the topic needs it: the second reason a reaction wants to go. In Example 1, decomposing ZnO releases free gas — a big jump in disorder. Multiply that by a high and it becomes a huge downhill push. Linked to Entropy and Temperature dependence of ΔG.


6. — Gibbs free energy change, the single verdict

Why "this tool and not another"? We need a single yes/no criterion for "does it go?". Neither alone nor alone decides it (a heat-releasing reaction can still be blocked by an ordering penalty). is the exact combination that gets the direction right every time. Full detail in Gibbs Free Energy.

Why the topic needs it: coupling is entirely a statement about signs — one positive, one negative, summing to negative.


7. State function — why we're even allowed to add

Why the topic needs it: THIS is the permission slip for "". Because only cares about endpoints, chaining reaction 1 into reaction 2 lets their 's add. This is exactly the reasoning behind Hess's Law.


8. Common intermediate — the shared "rope"

Why the topic needs it: it is the physical requirement for coupling to be legal. Without it, §7's "sum the steps" logic simply doesn't apply, because you don't have one continuous path.


9. Equilibrium constant — how far a reaction goes

Why the topic needs it: the parent's second punchline is . A tiny (reaction stalls) can be rescued by a huge . See Relation between ΔG and K.


10. , , and the bridge

Why and not something else? Because it is exactly the function that flips the additive world of into the multiplicative world of : Adding the 's and taking of both sides forces the 's to multiply. That's the whole reason "add G, multiply K" is true.


11. kJ/mol — the units

Why the topic needs it: every worked number (, , , ) is in these units — you must read the sign (down/up) and the size (how strong the push).


Prerequisite map

Energy uphill vs downhill

Delta G verdict

Delta means change

Delta H heat drive

Delta S disorder drive

Temperature T

Coupling reactions

State function

Delta G adds

Common intermediate

Equilibrium constant K

Delta G equals minus RT ln K

K multiplies


Equipment checklist

Test yourself — each line hides the answer.

What does the symbol in front of a quantity mean?
The change: final value minus initial value.
What does tell you about a reaction?
It runs forward on its own — it is spontaneous/favorable (downhill).
Write the formula linking , , , .
.
What is a state function, in one sentence?
A quantity depending only on start and end states, so its total change is the sum of the step changes.
Why does being a state function let coupled 's add?
Because only the endpoints matter, so chaining steps sums their — the shared intermediate cancels.
What is a common intermediate?
A molecule made by one reaction and consumed by the next, cancelling from the net equation.
What does vs tell you?
= mostly product (went far forward); = mostly reactant (barely happened).
State the bridge between and .
.
Why does turn "add the " into "multiply the "?
Because , so additive corresponds to multiplicative .
What does kJ/mol for ATP hydrolysis mean physically?
Each mole of ATP hydrolysed releases 30.5 kJ of free energy — a strongly downhill (favorable) reaction.

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