Irreversible reaction

Acetic acid and phosphorus trichloride to acetyl chloride and phosphorous acid

3C2H4O2+PCl33C2H3ClO+H3O3P

Direction
Irreversible
Processes
1
Stated as
Rate law
Heat of reaction
ΔH = -10,500 kJ/kmol (one process)
Element balance
Checked: balances
As the processes state itStoichiometry, conversions, heats of reaction and catalyst windows are taken from each process's files with their provenance. The build checks only that each process's equation balances in every element, from the process's own component formulas; it does not check the numbers. A process's design maturity applies to them.

Species

SpeciesNameCASRoleCoefficient
C2H4O2Acetic acid64-19-7reactant-3
PCl3Phosphorus trichloride7719-12-2reactant-1
C2H3ClOAcetyl chloride75-36-5product3
H3O3PPhosphorous acid (phosphonic acid)13598-36-2product1

In the processes

  • Acetyl chloride by semi-batch reaction of acetic acid with PCl3, phase split and batch distillation (2000 t/a)Concept · not reviewed

    ACCL · Acetic acid and phosphorus trichloride to acetyl chloride and phosphorous acid3 C2H4O2 + PCl3 → 3 C2H3ClO + H3PO3

    Stated as
    Rate law
    Phase
    liquid
    Element balance
    Balances in every element
    Heat of reaction
    ΔH = -10,500 kJ/kmol at 298.15 K, as written (assumed: derived from the CRC standard formation enthalpies packaged in chemicals 1.5.2 (3 x -272.9 - 964.4 + 3 x 484.3 + 319.7 = -10.5 kJ per mol PCl3) with phosphorous acid as the crystal; as a liquid (fusion 12.8 kJ/mol, chemicals 1.5.2) it is +2.3 kJ/mol, so the sign is uncertain and the exothermic bound is taken; no heat of mixing or solution in the two liquid phases (D-005))
    Rate law
    basis: volume; driving: concentration; form: power_law; k: {"A":"1.2046e5","Ea":50000}; orders: {"ACOH":1,"PCL3":1}; temperature range: 293.15 – 323.15 (assumed: ASSUMED effective rate (D-005): no open kinetics found (2026-11-05); k sized so that the post-reaction after the dosing reaches the target conversion of PCl3 in about the 30 min hold of CS 272 248 B2, Example 1; to be replaced by reaction calorimetry)

Sources

What the processes cite for this reaction, each source once: for the reaction itself, its conversion, its heat of reaction or its catalyst. As the processes write them; DOIs, US patent numbers and web addresses are linked.

  1. CS 272 248 B2 (Nitrokemia, 1991), Example 1: 1.0 mol PCl3 added to 3 mol acetic acid below 40 C, 30 min at 40-50 C, two phases settle

    For the reaction · cited by Acetyl chloride by semi-batch reaction of acetic acid with PCl3, phase split and batch distillation (2000 t/a)

  2. US 4 060 546 A (Henkel), background: PCl3 and anhydrous acetic acid in a 1:3 ratio

    For the reaction · cited by Acetyl chloride by semi-batch reaction of acetic acid with PCl3, phase split and batch distillation (2000 t/a)

  3. derived from the CRC standard formation enthalpies packaged in chemicals 1.5.2 (3 x -272.9 - 964.4 + 3 x 484.3 + 319.7 = -10.5 kJ per mol PCl3) with phosphorous acid as the crystal; as a liquid (fusion 12.8 kJ/mol, chemicals 1.5.2) it is +2.3 kJ/mol, so the sign is uncertain and the exothermic bound is taken; no heat of mixing or solution in the two liquid phases (D-005)

    For the heat of reaction · cited by Acetyl chloride by semi-batch reaction of acetic acid with PCl3, phase split and batch distillation (2000 t/a)