Home Work of (Physical Chemistry) at (28-12-2020)

Ayman Hammad Sabbar

Morning Study
Chemical Engineering – Oil & Gas Refining Dep. In U.O.T
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Solution 1 :
𝑷°
𝑨° 𝑷° 𝐥𝐧
𝑷𝒕
𝐥𝐧 = 𝒌𝒕 ⋯ ⋯ ⋯ → 𝐥𝐧 = 𝒌𝒕 ⋯ ⋯ ⋯ → 𝐤 =
𝑨𝒕 𝑷𝒕 𝒕
𝟎. 𝟑𝟓𝟔
𝒌= = 𝟑. 𝟓 × 𝟏𝟎−𝟒
𝟏𝟎𝟎𝟎
𝟎. 𝟕𝟏𝟕
𝒌= = 𝟑. 𝟓𝟖𝟓 × 𝟏𝟎−𝟒
𝟐𝟎𝟎𝟎
𝟏. 𝟎𝟕𝟕
𝒌= = 𝟑. 𝟓𝟗 × 𝟏𝟎−𝟒
𝟑𝟎𝟎𝟎
𝟏. 𝟒𝟑𝟕
𝒌= = 𝟑. 𝟓𝟗𝟐𝟓 × 𝟏𝟎−𝟒
𝟒𝟎𝟎𝟎

Solution 2 :
𝐥𝐧 𝑷𝒕 (𝐥𝐧 𝑷𝒕 ) × 𝟓 t 𝒕 ÷ 𝟏𝟎𝟎𝟎
2.03 10.15 1000 1
1.671 8.35 2000 2
1.311 6.55 3000 3
0.951 4.75 4000 4

𝐥𝐧 𝑷𝒕 = −𝒌𝒕 + 𝐥𝐧 𝑷°

∆𝒚 𝒚𝟐 − 𝒚𝟏
𝒔𝒍𝒐𝒑 (𝒎) = 𝑲 = ⋯⋯ → 𝑲 =
∆𝒙 𝒙𝟐 − 𝒙𝟏

(𝟖. 𝟑𝟓 − 𝟒. 𝟕𝟓) ÷ 𝟓
𝑲= = −𝟎. 𝟎𝟎𝟎𝟑𝟔
(𝟐 − 𝟒) × 𝟏𝟎𝟎𝟎
Sol:
For a first order reaction , half-life is not dependent on the concentration. in the given
situation , half-life varies with partial pressure of the gas (concentration), thus reaction
is not first order.
For a second order reaction the half-life depends on the initial concentration.
For a second order reaction....
𝟏
𝒕𝟎.𝟓 =
𝒌[𝑨]°
Since the partial pressure is directly proportional to the concentration....
𝟏 𝟏
𝒕𝟎.𝟓 = ⋯⋯⋯⋯⋯ → 𝑲 =
𝒌 𝑷° 𝒕𝟎.𝟓 𝑷°
𝟏
𝑲= = 𝟓. 𝟑 × 𝟏𝟎−𝟓 And for the second trial...
𝟑𝟒𝟎𝒔 ×𝟓𝟓.𝟓𝑲𝑷𝒂
𝟏
𝑲= = 𝟏. 𝟗 × 𝟏𝟎−𝟒
𝟏𝟕𝟖𝒔 × 𝟐𝟖. 𝟗𝑲𝑷𝒂

For a zero-order reaction....

[𝑨]° [𝑨]° 𝑷°
𝒕𝟎.𝟓 = ⋯⋯⋯⋯ → 𝑲 = ⋯⋯⋯ → 𝑲 =
𝟐𝒌 𝟐𝒕𝟎.𝟓 𝟐𝒕𝟎.𝟓
𝟓𝟓. 𝟓 𝑲𝑷𝒂
𝑲= = 𝟎. 𝟎𝟖𝟐
𝟐 × 𝟑𝟒𝟎𝒔

and for the second trial....

𝟐𝟖. 𝟗𝑲𝑷𝒂
𝑲= = 𝟎. 𝟎𝟖𝟐
𝟐 × 𝟏𝟕𝟖𝒔

The agreement for k is "close-enough" to say that the reaction is zero order