ABM Reyan Asim

CHM 2046
REMNOTE EXPORT

● 1) Thermodynamics language + big picture

○ Thermodynamics :: study of energy changes (heat + work) in chemical and physical
processes
○ System :: the part of the universe you are studying (reaction, solution, gas in a container)
○ Surroundings :: everything outside the system
○ Universe :: system + surroundings
○ Types of systems
■ Open system :: exchanges mass + energy
■ Closed system :: exchanges energy, not mass
■ Isolated system :: exchanges neither mass nor energy
○ Thermal equilibrium :: system and surroundings at the same temperature → no net heat
transfer
● 2) Heat vs Temperature
○ Temperature (T) :: measure of average kinetic energy of particles
○ Heat (q) :: energy transfer due to a temperature difference (flows hot → cold)
○ Energy units
■ Joule (J) :: SI unit
■ calorie (cal) :: 1 cal = 4.184 J
■ kilojoule (kJ) :: 1000 J
●
● 3) State functions vs path functions
○ State function :: depends only on initial and final state (path doesn’t matter)
■ Examples :: U, H, T, P, V
○ Path function :: depends on the path taken
■ Examples :: q, w
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● 4) First Law of Thermodynamics (Internal Energy)
○ First Law :: energy is conserved
○ Internal energy (U) :: total energy contained in a system
○ Change in internal energy :: ΔU = U_final − U_initial
○ Core equation :: ΔU = q + w
○ Sign conventions (chemistry)
■ Heat
● q > 0 :: system absorbs heat (endothermic)
● q < 0 :: system releases heat (exothermic)
■ Work
● w > 0 :: work done on the system
● w < 0 :: work done by the system
●
● 5) PV work (expansion/compression work)
○ PV work at constant external pressure :: w = −P_ext ΔV
■ Expansion: ΔV > 0 → w < 0 (system does work on surroundings)
■ Compression: ΔV < 0 → w > 0 (surroundings do work on system)
○ Constant volume case :: ΔV = 0 → w = 0 → ΔU = q_v
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● 6) Heat capacity & specific heat (temperature change calculations)
○ Temperature change :: ΔT = T_final − T_initial
○ Heat capacity (C) :: heat required to raise an object’s temperature by 1°C (or 1 K)
■ Equation :: q = C ΔT
○ Specific heat (c) :: heat required to raise 1 g by 1°C (or 1 K)
■ Equation :: q = m c ΔT
○ Molar heat capacity :: heat required to raise 1 mol by 1°C (or 1 K)
●
● 7) Calorimetry (solving for heat using temperature change)
 ○ Calorimetry :: measure heat transfer by measuring ΔT
○ Energy conservation idea :: total heat change in an isolated calorimetry setup sums to 0
○ Mixing / metal-in-water template
■ q_metal + q_water (+ q_calorimeter) = 0
■ For each part: q = m c ΔT
○ Reaction in solution (coffee-cup calorimeter, constant pressure)
■ q_solution = m_solution c_solution ΔT
■ q_rxn = −q_solution (if calorimeter heat is negligible)
○ Bomb calorimeter (constant volume)
■ q_v measures ΔU (not ΔH)
●
● 8) Phase changes + heating curves
○ During a phase change :: temperature stays constant (ΔT = 0), but heat is
absorbed/released
○ Heat (enthalpy) of fusion, ΔH_fus :: solid ⇄ liquid (per mol)
○ Heat (enthalpy) of vaporization, ΔH_vap :: liquid ⇄ gas (per mol)
○ Phase change equations
■ Melting/freezing :: q = n ΔH_fus
■ Boiling/condensing :: q = n ΔH_vap
○ Heating curve multi-step strategy
■ Break into segments and sum: q_total = q1 + q2 + q3 + …
■ Sloped segments (temperature changes) :: q = m c ΔT
■ Flat segments (phase changes) :: q = n ΔH_fus or q = n ΔH_vap
●
● 9) Enthalpy (H) and the key constant-pressure fix
○ Enthalpy definition :: H = U + PV
○ Change in enthalpy :: ΔH = H_products − H_reactants
○ Key relationship
■ At constant pressure (and only PV work): q_p = ΔH
■ Do NOT write “q = ΔH” unless you specify constant pressure
○ Relationship between ΔH and ΔU (constant pressure)
■ ΔH = ΔU + PΔV
■ If gases expand/contract a lot, ΔH and ΔU can differ noticeably
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● 10) Thermochemical equations (ΔH written with a balanced reaction)
○ Thermochemical equation :: balanced chemical equation + ΔH + phases (s, l, g, aq)
○ ΔH depends on
■ the balanced coefficients (amounts)
■ the direction of the reaction
■ physical states (phases)
○ Rules
■ Multiply reaction by factor k → multiply ΔH by k
■ Reverse reaction → change sign of ΔH
■ Add reactions → add their ΔH values
○ Mass → heat template
■ grams → moles of the substance used
■ use stoichiometry to connect to “moles of reaction”
■ scale ΔH accordingly (and keep sign)
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● 11) Hess’s Law (enthalpy of overall reaction)
○ Hess’s Law :: if a reaction happens in steps, ΔH_overall = Σ ΔH_steps
■ works because enthalpy is a state function
○ Hess’s Law algorithm
■ Write the target reaction
■ Flip given equations if needed (flip ΔH sign)
■ Multiply equations to match target coefficients (scale ΔH)
■ Add equations and cancel common species
■ Add ΔH values → ΔH_target
 ○ Energy level diagram idea
■ ΔH is the vertical difference between reactant and product “energy levels”
■ Multiple steps add to the same net vertical change
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● 12) Standard enthalpy of formation (ΔHf°) method
○ Standard enthalpy of formation, ΔHf° :: enthalpy change to form 1 mol of a compound
from its elements in their standard states
○ Important fact :: ΔHf° of an element in its standard state = 0
○ Reaction enthalpy from formation enthalpies
■ ΔH_rxn° = Σ(n·ΔHf° products) − Σ(n·ΔHf° reactants)
■ n = stoichiometric coefficient in the balanced equation
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● 13) Product-favored vs reactant-favored (thermo preview idea)
○ Product-favored reaction :: equilibrium mixture contains mostly products
○ Reactant-favored reaction :: equilibrium mixture contains mostly reactants
○ Often (not always): exothermic reactions tend to be more product-favored than
endothermic ones under the same conditions
● Summary
● Core equations
○ ΔU = q + w
○ w = −P_ext ΔV
○ q = m c ΔT
○ q = C ΔT
○ Phase changes: q = nΔH_fus, q = nΔH_vap
○ H = U + PV
○ Constant pressure: q_p = ΔH
○ Constant volume: q_v = ΔU
○ ΔH_rxn° = Σ(nΔHf° products) − Σ(nΔHf° reactants)
○ Hess’s Law: ΔH_target = ΣΔH_steps
● Sign conventions (chem)
○ Endothermic: q > 0 (system absorbs heat)
○ Exothermic: q < 0 (system releases heat)
○ Expansion: ΔV > 0 → w < 0
○ Compression: ΔV < 0 → w > 0
● Quick “what do I use?”
○ Temperature change only → q = mcΔT
○ Phase change only → q = nΔH_fus or nΔH_vap
○ Coffee-cup calorimeter (constant pressure) → q_p relates to ΔH
○ Bomb calorimeter (constant volume) → q_v relates to ΔU
○ Need ΔH of a reaction → Hess’s Law OR formation enthalpies
● Hess’s Law mini-checklist
○ Flip? → flip ΔH sign
○ Multiply? → multiply ΔH
○ Add equations → add ΔH values