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(1)

1

宣道中學

化學測驗

化學動力學

S.6S

13/10/2008

1.

將一小塊銅(copper)放入 35°

C 的稀硝酸(dilute nitric acid)中,反應進行較慢,有

氣泡(effervescent)產生及生成一藍色溶液。

(a)

寫出銅與稀硝酸反應的離子方程式(ionic equation)。

(b)

試述增加此反應的速率(rate of reaction)的三種方法。

(c)

試述下列的改變,哪個最能增加反應速率(reaction rate)?

(i)

增加酸的濃度一倍

(ii)

增加酸的體積一倍

(iii)

增加溫度一倍

哪個對反應的起始速率並無影響?

2.

某 學 生 在 20°

C 進 行 一 實 驗 , 以 研 究 硫 代 硫 酸 鈉 ( sodium thiosulphate ) 濃 度

(concentration)對下列反應速率(reaction rate)的影響:

S2O3

2-

(aq) + 2H

+

(aq)

→

H2O(g) + SO2(aq) + S(s)

該學生按下所列的分量,在類似的燒杯中製備四個硫代硫酸鈉溶液的樣本。他把盛有

樣本 I 的燒杯放在一個黑色 「

「+」

」 字記號上,然後加入 20 cm

3

的 2 M HCl,並記錄記

號從視線中消失所需的時間 t。他用其餘樣本重複這實驗,所得結果如下:

樣本的成分

樣本

0.1

M 硫代硫酸鈉

溶液的體積 /cm

3

水的體積

/cm

3

t (s)

1/t /s

-1

I

20.0

0.0

37

0.0270

II

15.0

5.0

50

0.0200

III

10.0

10.0

76

0.0133

IV

5.0

15.0

154

0.0065

(2)

2

2.

(a)

試解釋下列各題:

(i)

製備樣本 II,III 和 IV 時,須把水加入硫代硫酸鈉溶液中。

(ii)

燒杯須放置在一個黑色十字記號上。

(iii)

t 秒後黑色十字記號會從視線中消失。

(iv)

各樣本中須用相同體積的酸。

1

(b) 繪出所用 0.1 M 硫代硫酸鈉溶液的體積對

t

的座標圖(graph)。

(c)

若把 20 cm

3

的 2 M HCl 加入一含有 16 cm

3

的 0.1 M 硫代硫酸鈉溶液和 4 cm

3

的樣本時。試利用你所給繪的座標圖推測記號消失所需的時間。

(d) 硫代硫酸鈉溶液的濃度和反應速率有甚麼關係?試利用所繪的座標圖以解釋你的

答案。

3.

(a)

解釋「速率方程式」(rate equation)、「反應級數」(rate order)和「速率常數」

(rate constant)這些詞彙(glossary)的意思。

(b)

乙酸乙酯(ethyl ethanoate)在酸性水溶液(aqueous acidic solution)中的水解反應

(hydrolysis)可以用以下化學方程式表示:

CH

3

CO

2

C

2

H

5

+ H

2

O

HCl

 →

CH

3

CO

2

H + CH

3

OH

以下是此反應在使用不同濃度的氫氯酸(hydrochloric acid)時所得的數據:

時間

使用 0.1 M HCl

時乙酸乙酯的

濃度(mol dm

-3

使用 0.2 M HCl

時乙酸乙酯的

濃度(mol dm

-3

0

0.200

0.200

25

0.152

0.115

50

0.115

0.067

75

0.088

0.038

100

0.067

0.022

125

0.051

0.013

(i)

利用以上數據,繪畫乙酸乙酯的濃度對時間的線圖。

(ii) 利用 (i) 的線圖,

(1) 證明乙酸乙酯的反應級數是一級的;

(2) 計算氫氯酸的反應級數。

(iii) 推斷此反應的速率方程式,並計算其速率常數(附上單位)。

(c)

為甚麼在此實驗中不能夠測定水的反應級數?

(3)

3

4.

氰化氫(hydrogen cyanide)在水溶液中轉化為甲酸銨(ammonium methanoate)的過程如

下化學方程式所示:

HCN(aq) + 2H2O(ℓ)

→

HCOONH4(aq)

在 330 K 時,該反應的速率方程式(rate equation)是:

t

)]

[HCN(

d

aq

d

= 8

×

10

-8

[HCN(aq)]

其中 k 以 s

-1

為單位。

(a)

計算該反應的半衰期(half-life time)。

(4)

4

1.

(a)

2Cu(s) + 8H

+

(aq) + 2NO3

-

(aq)

→

3Cu

2+

(aq) + 4H2O(ℓ) + 2NO(g)

(b)



增加 HNO3 濃度



用銅粉代替銅塊



加熱

(c)

(i)

最能增加反應速率

(ii)

對反應的起始速率並無影響

2.

(a)

(i)

保證每次實驗的溶液體積 (高度) 相同。

(ii)

作為觀察該記號消失所需時間的標準。

(iii)

當生成足夠的一定量膠質硫時,該記號便會從視線中消失。

(iv)

保證每次實驗中 HCl 的濃度相同,唯一的變項是硫代硫酸鈉的濃度。

(b)

(c)

由圖: 1/t = 2.15×

10

-2

s

-1

所需時間 = 46.5 s

(d) 0.1 M 硫代硫酸鈉的體積與其在混合溶液中的濃度成正比。

1/t 與反應速率成正比。

所以反應速率與硫代硫酸鈉濃度成正比,硫代硫酸鈉濃度愈高,反應速率愈快。

3. (a) Rate equation is an equation that relates the reaction rate to the concentrations of the reactants. Order of a reaction with respect to a reactant refers to the power to which the concentration of the

reactant is raised in a rate equation. The overall order of reaction is the sum of all the powers to which the concentrations of the reactants are raised in the rate equation.

Rate constant is a constant of proportionality between the reaction rate and the concentrations of reactants that appear in the rate equation.

Hence, for the reaction A + B → C, if the rate is first order with respect to A and B, then the rate equation is Rate = k[A][B]. Overall order of reaction is 1 + 1 = 2 and rate constant = k.

(5)

5

(b) (i) Graph A: [ethyl ethanoate] against time with [HCl] = 0.1 mol dm−3

Graph B: [ethyl ethanoate] against time with [HCl] = 0.2 mol dm−3

(ii) From graph A, it is seen that the half-life is a constant. Hence, the rate of reaction is first

order with respect to ethyl ethanoate. Since HCl is a catalyst, [HCl] is a constant. Let the order of reaction with respect to HCl be a.

Hence, the rate equation is Rate = k[ethyl ethanoate][HCl]a. For the first experiment,

Initial rate, Ri1 = k[0.200][0.1]a = slope of graph A at t = 0 min = 1.9 × 10−3 mol dm−3 min−1 For the second experiment,

Initial rate, Ri2 = k[0.200][0.2]a = slope of graph B at t = 0 min = 3.8 × 10−3 mol dm−3 min−1 2 1 i i R R : a a 2 . 0 1 . 0 = 3 3 10 8 . 3 10 9 . 1 − − × × ⇒ a = 1

(iii) Rate equation: Rate = k[ethyl ethanoate][HCl]

Rate constant, k = [HCl] 2 In 2 1 t = 62 0.1 2 In × = 0.112 min− 1

(c) Water is used as a solvent , so its concentration is very high and remains approximately constant as the reaction proceeds.

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