K I N ET I C S OF A H E T ER O GE N EO U S R EA C TI ON:

O X I DA T I O N O F M AG N ES I U M B Y H Y DR OC H LOR I C A C I D
Objective (1)
The objective of this experiment is to determine the order of reaction and rate constant for the oxidation of
magnesium by hydrochloric acid. The overall reaction is given as

Mg(s) + 2H3 O+ (aq) → Mg 2+ (aq) + H2 (g) + 2H2 O(l), [1]

where elemental magnesium is oxidized by hydrochloric acid to produce hydrogen gas. Determining the rate
constant and order of reaction is important in sizing and determining optimal operating conditions for reactors. This
reaction occurs spontaneously due to the difference in standard reduction potential of magnesium and hydrogen. The
reaction kinetics is determined from the reaction velocity, which is the change in partial pressure of hydrogen with
respect to time,

dPH2 α [H + ]β
V= = kSMg , [2]
dt

where the reaction velocity is a function of the magnesium surface area, S Mg, and concentration of hydronium ion,
H+. To calculate the value of the rate constant, the order of the reaction with respect to surface area and
concentration is determined from the initial-rate method, where the initial rate of reaction is given by

β
V0 = k′[H + ]0 [3]

α
V0 = k′SMg,0 [4]

where V0 is the initial reaction velocity and k’ is the effective rate constant. Using equation 3 and 4 the values of β
and α can be found using constant surface area and constant hydronium, respectively.

Experimental Details (1)

The experiment followed the method for experiment 25 outlined in the Physical Chemistry Laboratory II textbook
for constant T while varying [H+] and SMg.

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Data
The experiment was run at 21°C.

Table 1: Initial conditions for each run

Run Molarity of HCl (M) Length of Mg (cm) Initial Pressure (kPa)

1 0.2 1.0 104.42
2 0.5 1.0 102.33
3 1.0 1.0 101.09
4 1.0 0.5 102.27
5 1.0 2.0 101.77

Table 2: Partial pressure of H2 for each run in torr

Time (s) Run 1 Run 2 Run 3 Run 4 Run 5

0 0.00 0.00 0.00 0.00 0.00
1 0.00 0.00 11.40 2.55 2.48
2 0.45 0.45 13.58 4.28 4.65
3 0.83 0.45 19.05 5.55 8.03
4 0.45 0.45 23.33 6.83 9.30
5 0.83 0.83 26.70 8.10 11.85
6 0.83 0.83 29.63 9.38 13.13
7 0.83 1.28 32.18 10.65 15.23
8 1.28 1.73 36.00 11.48 16.50
9 1.28 1.73 39.83 12.75 18.23
10 1.28 2.10 43.20 14.03 19.43
11 1.73 2.10 47.03 14.85 21.15
12 1.73 2.10 50.85 16.13 22.88
13 1.73 2.55 54.68 17.85 24.98
14 2.10 2.55 58.43 19.50 26.25
15 2.10 3.00 62.26 20.78 27.90
16 2.55 3.00 66.08 22.95 29.18
17 2.55 3.38 69.46 24.60 30.45
18 2.10 3.38 72.91 26.33 31.73
19 2.55 3.38 76.28 28.43 33.00
20 2.55 3.83 80.11 30.53 34.28

2
Calculations (1)
Sample calculation for the partial pressure of H2 in torr using run 1 at 20 s

760 torr
Partial pressure = (Total pressure − Initial pressure) ∙
101.325 kPa
760
Partial pressure = (104.76 − 104.42) ∙ = 2.55 torr
101.325

Sample calculation for k using run 1

V
k= α
SMg [H + ]β

0.13 torr
k= = 0.0413 2
801 1.02 M mm2 s

Average k values

k1 + k 2 + k 3 + k 4 + k 5
k avg =
5
0.0413 + 0.0098 + 0.0465 + 0.0351 + 0.0105 torr
k avg = = 0.0286 2
5 M mm2 s

Sample calculation for relative error of k

Experimental − Literature value

% Error = (| |) × 100%
Literature value
0.0286 − 0.0272
% Error = (| |) × 100% = 5.31%
0.0272

Calculation for standard deviation, using N=5 and kavg=0.0286

N
1
σ = √ ∑(k i − k avg )2
N
i=1

σ = 0.0156

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Graphs
90
y = 0.1323x + 0.0916
80
y = 0.1955x - 0.0942
70
y = 3.7225x + 6.2495
60
y = 1.4047x + 0.5975
PH2 (torr)
50
y = 1.6728x + 2.3482
40
30
20
10
0
0 5 10 15 20
Time (s)

Run 1 Run 2 Run 3 Run 4 Run 5

Figure 1: Linear regression of initial rates of reaction

The partial pressure of hydrogen was plotted against time (Figure 1) to calculate the initial velocity for each run. The
initial slope in torr/s for runs 1-5 were 0.132, 0.196, 3.723, 1.405 and 1.673, respectively.

0.8
0.6
0.4
y = 1.9873x + 0.3236
0.2
0
log(V0)

-0.2
-0.4
-0.6
-0.8
-1
-1.2
-0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0
log([H+])

Figure 2: Determination of β from log(V0) vs. log([H+]) plot

To calculate the value of β, the values of V0 and [H+] from runs 1, 2 and 3 were plotted on a logarithmic scale. The
value of β is determined to be 2.

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 0.6

0.5

y = 1.0078x - 1.632
0.4
log(V0)
0.3

0.2

0.1

0
1.5 1.7 1.9 2.1 2.3
log(SMg)

Figure 3: Determination of α from log(V0) vs. log(SMg) plot

To calculate the value of α, the values of V0 and SMg from runs 3, 4 and 5 were plotted on a logarithmic scale. The
value of α is determined to be 2.

Summary of Results
Table 3: Values from figure 2 and figure 3

Run [H+] (M) Surface Area (mm2) Initial Velocity (torrs-1) k (torrM-2mm-2s-1)
1 0.2 80 0.132 0.0413
2 0.5 80 0.196 0.0098
3 1.0 80 3.723 0.0465
4 1.0 40 1.405 0.0351
5 1.0 160 1.673 0.0105

Table 4: Comparison of experimental rate constant to literature value

Experimental Value Literature Value (1) Relative Error (%)

k (torrM-2mm-2s-1) 0.0286 ± 0.0156 0.0272 5.31

Discussion
In run 2, the oxide layer was not removed from the strip which resulted in a lower initial velocity and lower rate
constant. In run 1, the magnesium strip was folded in half and the surface area was smaller than 80 mm 2, this
resulted in a slower initial velocity.

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Question for further thought
In the reaction between magnesium oxide and hydrochloric acid

MgO + 2HCl  MgCl2 + H2O

is a neutralization reaction which produces a soluble salt and water (2). The oxide neutralizes the hydrochloric acid
and creates water, thus creating less hydrogen gas. The outcome is a decrease in the reaction velocity and rate
constant.

C&EN Abstract (3)

Ceres is a dwarf planet that resides inside of Neptune’s orbit, in which small amounts of hydrated sodium carbonates
were found and suggest that liquid water has flowed near the plant’s surface. Researchers at the Institute for Space
Astrophysics and Planetology have proposed two ways these hydrated sodium carbonates could be found on the
planet. The planet may have a subsurface ocean, where the brine from the ocean seeps upwards and through cracks
in the crust. Alternately, meteor impacts could melt frozen brine below the surface. In either case, because hydrated
carbonates are unstable on the surface of the plant, the hydration is believed to be occurring today.

References
1. Chemistry Department University of Mass. Physical Chemistry: Laboratory II. New York : W.H. Freeman &
Company, 2016.

2. Tro, Nivaldo J. Chemistry: Structure and Properties. s.l. : Pearson Education, Inc., 2015.

3. Carbonates hint at liquid. Lemonick, Sam. 12, s.l. : American Chemical Society, March 19, 2018, C&EN, Vol.
96, p. 5.

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Appendix
Table 5: Sample total pressure data in kPa up to 20s

Time (s) Run 2 Run 3 Run 4 Run 5 Run 1

0 102.33 101.09 102.27 101.77 104.42
0.5 102.33 102.22 102.56 101.93 104.48
1 102.33 102.61 102.61 102.10 104.42
1.5 102.33 102.84 102.73 102.22 104.48
2 102.39 102.90 102.84 102.39 104.48
2.5 102.39 103.18 102.95 102.61 104.48
3 102.39 103.63 103.01 102.84 104.53
3.5 102.39 104.03 103.06 102.90 104.48
4 102.39 104.20 103.18 103.01 104.48
4.5 102.39 104.48 103.23 103.18 104.53
5 102.44 104.65 103.35 103.35 104.53
5.5 102.44 104.82 103.40 103.40 104.53
6 102.44 105.04 103.52 103.52 104.53
6.5 102.50 105.21 103.63 103.63 104.53
7 102.50 105.38 103.69 103.80 104.53
7.5 102.50 105.66 103.74 103.91 104.53
8 102.56 105.89 103.80 103.97 104.59
8.5 102.50 106.12 103.91 104.08 104.59
9 102.56 106.40 103.97 104.20 104.59
9.5 102.56 106.62 104.03 104.31 104.59
10 102.61 106.85 104.14 104.36 104.59
10.5 102.61 107.13 104.14 104.48 104.65
11 102.61 107.36 104.25 104.59 104.65
11.5 102.61 107.64 104.31 104.70 104.65
12 102.61 107.87 104.42 104.82 104.65
12.5 102.61 108.09 104.48 104.93 104.70
13 102.67 108.38 104.65 105.10 104.65
13.5 102.67 108.60 104.76 105.16 104.70
14 102.67 108.88 104.87 105.27 104.70
14.5 102.67 109.11 104.99 105.38 104.70
15 102.73 109.39 105.04 105.49 104.70
15.5 102.73 109.62 105.16 105.55 104.7
16 102.73 109.9 105.33 105.66 104.76
16.5 102.78 110.13 105.44 105.72 104.7
17 102.78 110.35 105.55 105.83 104.76
17.5 102.78 110.64 105.66 105.95 104.76
18 102.78 110.81 105.78 106 104.7
18.5 102.78 111.03 105.95 106.06 104.76
19 102.78 111.26 106.06 106.17 104.76
19.5 102.84 111.48 106.17 106.29 104.76
20 102.84 111.77 106.34 106.34 104.76

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