H2SO4 + KMnO4 + C4H6 = H2O + CO2 + K2SO4 + MnSO4 + H2C2O4

H_2SO_4 sulfuric acid + KMnO_4 potassium permanganate + CH_2=CHCH=CH_2 1, 3-butadiene ⟶ H_2O water + CO_2 carbon dioxide + K_2SO_4 potassium sulfate + MnSO_4 manganese(II) sulfate + HO_2CCO_2H oxalic acid

Balance the chemical equation algebraically: H_2SO_4 + KMnO_4 + CH_2=CHCH=CH_2 ⟶ H_2O + CO_2 + K_2SO_4 + MnSO_4 + HO_2CCO_2H Add stoichiometric coefficients, c_i, to the reactants and products: c_1 H_2SO_4 + c_2 KMnO_4 + c_3 CH_2=CHCH=CH_2 ⟶ c_4 H_2O + c_5 CO_2 + c_6 K_2SO_4 + c_7 MnSO_4 + c_8 HO_2CCO_2H Set the number of atoms in the reactants equal to the number of atoms in the products for H, O, S, K, Mn and C: H: | 2 c_1 + 6 c_3 = 2 c_4 + 2 c_8 O: | 4 c_1 + 4 c_2 = c_4 + 2 c_5 + 4 c_6 + 4 c_7 + 4 c_8 S: | c_1 = c_6 + c_7 K: | c_2 = 2 c_6 Mn: | c_2 = c_7 C: | 4 c_3 = c_5 + 2 c_8 Since the coefficients are relative quantities and underdetermined, choose a coefficient to set arbitrarily. To keep the coefficients small, the arbitrary value is ordinarily one. For instance, set c_5 = 1 and solve the system of equations for the remaining coefficients: c_2 = (2 c_1)/3 c_3 = (5 c_1)/27 - 1/18 c_4 = (32 c_1)/27 + 4/9 c_5 = 1 c_6 = c_1/3 c_7 = (2 c_1)/3 c_8 = (10 c_1)/27 - 11/18 Multiply by the least common denominator, 2, to eliminate fractional coefficients: c_2 = (2 c_1)/3 c_3 = (5 c_1)/27 - 1/9 c_4 = (32 c_1)/27 + 8/9 c_5 = 2 c_6 = c_1/3 c_7 = (2 c_1)/3 c_8 = (10 c_1)/27 - 11/9 The resulting system of equations is still underdetermined, so an additional coefficient must be set arbitrarily. Set c_1 = 33 and solve for the remaining coefficients: c_1 = 33 c_2 = 22 c_3 = 6 c_4 = 40 c_5 = 2 c_6 = 11 c_7 = 22 c_8 = 11 Substitute the coefficients into the chemical reaction to obtain the balanced equation: Answer: | | 33 H_2SO_4 + 22 KMnO_4 + 6 CH_2=CHCH=CH_2 ⟶ 40 H_2O + 2 CO_2 + 11 K_2SO_4 + 22 MnSO_4 + 11 HO_2CCO_2H

+ + ⟶ + + + +

sulfuric acid + potassium permanganate + 1, 3-butadiene ⟶ water + carbon dioxide + potassium sulfate + manganese(II) sulfate + oxalic acid

Construct the equilibrium constant, K, expression for: H_2SO_4 + KMnO_4 + CH_2=CHCH=CH_2 ⟶ H_2O + CO_2 + K_2SO_4 + MnSO_4 + HO_2CCO_2H Plan: • Balance the chemical equation. • Determine the stoichiometric numbers. • Assemble the activity expression for each chemical species. • Use the activity expressions to build the equilibrium constant expression. Write the balanced chemical equation: 33 H_2SO_4 + 22 KMnO_4 + 6 CH_2=CHCH=CH_2 ⟶ 40 H_2O + 2 CO_2 + 11 K_2SO_4 + 22 MnSO_4 + 11 HO_2CCO_2H Assign stoichiometric numbers, ν_i, using the stoichiometric coefficients, c_i, from the balanced chemical equation in the following manner: ν_i = -c_i for reactants and ν_i = c_i for products: chemical species | c_i | ν_i H_2SO_4 | 33 | -33 KMnO_4 | 22 | -22 CH_2=CHCH=CH_2 | 6 | -6 H_2O | 40 | 40 CO_2 | 2 | 2 K_2SO_4 | 11 | 11 MnSO_4 | 22 | 22 HO_2CCO_2H | 11 | 11 Assemble the activity expressions accounting for the state of matter and ν_i: chemical species | c_i | ν_i | activity expression H_2SO_4 | 33 | -33 | ([H2SO4])^(-33) KMnO_4 | 22 | -22 | ([KMnO4])^(-22) CH_2=CHCH=CH_2 | 6 | -6 | ([CH2=CHCH=CH2])^(-6) H_2O | 40 | 40 | ([H2O])^40 CO_2 | 2 | 2 | ([CO2])^2 K_2SO_4 | 11 | 11 | ([K2SO4])^11 MnSO_4 | 22 | 22 | ([MnSO4])^22 HO_2CCO_2H | 11 | 11 | ([HO2CCO2H])^11 The equilibrium constant symbol in the concentration basis is: K_c Mulitply the activity expressions to arrive at the K_c expression: Answer: | | K_c = ([H2SO4])^(-33) ([KMnO4])^(-22) ([CH2=CHCH=CH2])^(-6) ([H2O])^40 ([CO2])^2 ([K2SO4])^11 ([MnSO4])^22 ([HO2CCO2H])^11 = (([H2O])^40 ([CO2])^2 ([K2SO4])^11 ([MnSO4])^22 ([HO2CCO2H])^11)/(([H2SO4])^33 ([KMnO4])^22 ([CH2=CHCH=CH2])^6)

Construct the rate of reaction expression for: H_2SO_4 + KMnO_4 + CH_2=CHCH=CH_2 ⟶ H_2O + CO_2 + K_2SO_4 + MnSO_4 + HO_2CCO_2H Plan: • Balance the chemical equation. • Determine the stoichiometric numbers. • Assemble the rate term for each chemical species. • Write the rate of reaction expression. Write the balanced chemical equation: 33 H_2SO_4 + 22 KMnO_4 + 6 CH_2=CHCH=CH_2 ⟶ 40 H_2O + 2 CO_2 + 11 K_2SO_4 + 22 MnSO_4 + 11 HO_2CCO_2H Assign stoichiometric numbers, ν_i, using the stoichiometric coefficients, c_i, from the balanced chemical equation in the following manner: ν_i = -c_i for reactants and ν_i = c_i for products: chemical species | c_i | ν_i H_2SO_4 | 33 | -33 KMnO_4 | 22 | -22 CH_2=CHCH=CH_2 | 6 | -6 H_2O | 40 | 40 CO_2 | 2 | 2 K_2SO_4 | 11 | 11 MnSO_4 | 22 | 22 HO_2CCO_2H | 11 | 11 The rate term for each chemical species, B_i, is 1/ν_i(Δ[B_i])/(Δt) where [B_i] is the amount concentration and t is time: chemical species | c_i | ν_i | rate term H_2SO_4 | 33 | -33 | -1/33 (Δ[H2SO4])/(Δt) KMnO_4 | 22 | -22 | -1/22 (Δ[KMnO4])/(Δt) CH_2=CHCH=CH_2 | 6 | -6 | -1/6 (Δ[CH2=CHCH=CH2])/(Δt) H_2O | 40 | 40 | 1/40 (Δ[H2O])/(Δt) CO_2 | 2 | 2 | 1/2 (Δ[CO2])/(Δt) K_2SO_4 | 11 | 11 | 1/11 (Δ[K2SO4])/(Δt) MnSO_4 | 22 | 22 | 1/22 (Δ[MnSO4])/(Δt) HO_2CCO_2H | 11 | 11 | 1/11 (Δ[HO2CCO2H])/(Δt) (for infinitesimal rate of change, replace Δ with d) Set the rate terms equal to each other to arrive at the rate expression: Answer: | | rate = -1/33 (Δ[H2SO4])/(Δt) = -1/22 (Δ[KMnO4])/(Δt) = -1/6 (Δ[CH2=CHCH=CH2])/(Δt) = 1/40 (Δ[H2O])/(Δt) = 1/2 (Δ[CO2])/(Δt) = 1/11 (Δ[K2SO4])/(Δt) = 1/22 (Δ[MnSO4])/(Δt) = 1/11 (Δ[HO2CCO2H])/(Δt) (assuming constant volume and no accumulation of intermediates or side products)

| sulfuric acid | potassium permanganate | 1, 3-butadiene | water | carbon dioxide | potassium sulfate | manganese(II) sulfate | oxalic acid formula | H_2SO_4 | KMnO_4 | CH_2=CHCH=CH_2 | H_2O | CO_2 | K_2SO_4 | MnSO_4 | HO_2CCO_2H Hill formula | H_2O_4S | KMnO_4 | C_4H_6 | H_2O | CO_2 | K_2O_4S | MnSO_4 | C_2H_2O_4 name | sulfuric acid | potassium permanganate | 1, 3-butadiene | water | carbon dioxide | potassium sulfate | manganese(II) sulfate | oxalic acid IUPAC name | sulfuric acid | potassium permanganate | buta-1, 3-diene | water | carbon dioxide | dipotassium sulfate | manganese(+2) cation sulfate | oxalic acid