HDC2 Solution
HDC2 Solution
HDC2 Solution
vn
UNIVERSITY OF SCIENCE, HCM CITY FACULTY OF CHEMISTRY (nếu cần lời giải cho các câu không có)
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CHAPTER 1. THERMOCHEMISTRY
Q.1 (EX7-1A) How much heat, in kilojoules (kJ), is required to raise the temperature of 237 g of cold water
from 4.0 to 37.0 °C (body temperature)? (CH2O = 4,18 J/g oC)
Ans
4,18 J 1 kJ
qcold water = 237gam cold water . . (37 − 4)℃. = 32,7 kJ
gam cold water . ℃ 1000 J
Q.2 (EX7-1B) How much heat, in kilojoules (kJ), is required to raise the temperature of 2.50 kg Hg(l) from
–20.0 oC to –6.0 oC? Assume a density of 13.6 g/mL and a molar heat capacity of 28.0 J.mol-1 °C–1 for Hg(l)
Ans
1000g 1 mol 28,0J kJ
qHg(l) = 2,50 kg Hg(l). . . . [−6 − (−20,0)]℃. = 4,89 kJ
kg Hg(l) 200,59. g Hg(l) 𝑚𝑜𝑙. ℃ 1000J
Q.3 (EX7-2A) When 1.00 kg lead (specific heat = 0.13 J g–1 oC –1) at 100.0 oC is added to a quantity of water
at 28.5 oC, the final temperature of the lead-water mixture is 35.2 oC. What is the mass of water present?
Ans
1000 g 0,13. J
qlead = 1,00 kg lead. . . (35,2 − 100)℃ = −8424J
kg g. ℃
We can write: qlead = −qwater = 8424J
Now, we obtain: qwater = m gam water. specific heat of lead . (t lead−water − t water )℃
4,18J
⇔ 8424J = m water. . (35,2 − 28,5)℃ ⇒ m = 300,8 (g)
gam water. ℃
Q.4 A 100.0g copper sample (specific heat = 0.385 Jg-1°C -1) at 100.0 °C is added to 50.0 g water at 26.5 °C.
What is the final temperature of the copper-water mixture?
Ans
4,18 J
Nhiệt dung riêng của 1.00 g nước là
g.nước.℃
0,385 J
qđồng = 100 g đồng . . ( t đồng−nước − 100)℃ = 38,5( t đồng−nước − 100)J
g. đồng. ℃
4,18 J
qnước = 50,0 g nước . . ( t đồng−nước − 26,5)℃ = 209 ( t đồng−nước − 26,5) J
g. nước. ℃
Ta có: qđồng = −qnuớc ⇔ 38,5( t đồng−nước − 100) = −209 ( t đồng−nước − 26,5)
⇒ t đồng−nước = 37,93℃
Q.5 (EX7-3A) Vanillin is a natural constituent of vanilla. It is also manufactured for use in artificial vanilla
flavoring. The combustion of 1.013 g of vanillin, C8H8O3, in a bomb calorimeter causes the temperature to
rise from 24.89 to 30.09 oC. What is the heat of combustion of vanillin, expressed in kilojoules per mole?
(the heat capacity of the calorimeter assembly is 4.90 kJ/oC).
Ans
4,90 kJ −qcal kJ. 152,141g/mol kJ
qcal = . (30,09 − 24,89)℃ = 25,48 → qvanillin = = −3,83.103 .
℃ 1,013g mol
Q.6 (EX7-3B) The heat of combustion of benzoic acid is –26.42 kJ/g. The combustion of a 1.176 g sample
of benzoic acid causes a temperature increase of 4.96 oC in a bomb calorimeter assembly. What is the heat
capacity of the assembly?
Ans
kJ
qcal = −qbenzoic = 26,42 . 1,176g = 31,1kJ
g
31,1kJ
Ta có: qcal = Ccal . ∆t → Ccal = = 6,264kJ
4,96℃
Q.7 (EX7-4A) Two solutions, 100.0 mL of 1.00 M AgNO3(aq) and 100.0 mL of 1.00 M NaCl(aq), both
initially at 22.4 oC, are added to a Styrofoam-cup calorimeter and allowed to react. The temperature rises to
30.2 oC. Determine qrxn per mole of in the reaction.
Ag+ (aq) + Cl-(aq) → AgCl(s)
Ans
We begin with:
1,00g 4,18J
qcal = 200mL. . . (30,2 − 22,4)℃ = 6520,8J = 6,52 kJ
mL g. ℃
qneutr = −qcalorim = −6,52 kJ
qneutr −6,52kJ.
∆H = = = −65,2kJ. mol−1
nAgCl 0,1.1. mol
Q.8 (EX7-4B) Two solutions, 100.0mL of 1.020 M HCl and 50.0 mL of 1.988 M NaOH, both initially at
24.52 oC, are mixed in a Styrofoam-cup calorimeter and allowed to react. What will be the final temperature
of the mixture? The heat of neutralization reaction is –56 kJ/mol H2O
Ans
H + (aq) + OH − (aq) → H2 O(l)
We begin with:
1,00g 4,18 J
qcal = 150mL. . . (t final − 24,52)℃ = 627. (t final − 24,52)J
mL g. ℃
qneutr = −qcal = −627. (t final − 24,52)J
In 25.00 mL of 2.50 M HCl, the amount of H+ is:
+
1L 1,020 mol 1 mol H +
? mol H = 100,0mL. . . = 0,102 mol H +
1000mL 1L 1 mol HCl
Similarly, in 50,0 mL of 1,988M NaOH there is 0,0994 mol OH-. So the number of moles of water produced
is equal to the number of moles of OH-.
The amount of heat produced per mole of is -56 kJ/mol H2O
1000J −627. (t final − 24,52)J
→ −56kJ. mol−1 . = qneutr = ⇒ t final = 33,4℃
kJ 0,0994 mol
Q.9 (EX7-5A) How much work, in joules, is involved when 0,225 mol N2 at a constant temperature of 23℃
is allowed to expand by 1.50 L in volume against an external pressure of 0.750 atm?
Ans
101 J
W = −P. ∆V = −0,75 atm . 1,50 L . = −114 J
1. L. atm
Q.10 (EX7-5B) How much work is done, in joules, when an external pressure of 2.50 atm is applied, at a
constant temperature of to 20.0 °C, to 50.0 g N2(g) in a 75.0 L cylinder?
Ans
50 −1 −1
nRT 28,014 . mol. 0,082. L. atm. K . mol . 293K
V= = = 17,15 L
P 2,5atm
101J kJ
W = −P. ∆V = −2,5atm. (17,15 − 75)L. . = 14,6 kJ
1. L. atm 1000J
Q.11 (EX7-6A) In compressing a gas, 355 J of work is done on the system. At the same time, 185 J of heat
escapes from the system. What is ΔU for the system?
Ans
∆U = q + W = 355J − 185J = 170J
Q.12 (EX7-6B) If the internal energy of a system decreases by 125 J at the same time that the system absorbs
54 J of heat, does the system do work or have work done on it? How much?
Ans
As the internal energy of the system decreases so the system do work.
∆U = q + W ⇔ −125J = 54J + W ⇒ W = −179J
Q.13 (EX7-7A) What mass of sucrose must be burned to produce 1.00 ×103 kJ of heat? The heat of
combustion of sucrose is –5,65 ×103 kJ/mol sucrose.
Ans
−q 3
5,65.103 . msucrose
∆H = ⇔ 1,00.10 = ⇒ msucrose = 60,6 gam
mol 342,285
Q.14 (EX7-7B) A 25.0 mL sample of 0.1045 M HCl(aq) was neutralized by NaOH(aq). Determine the heat
evolved in this neutralization. The heat of neutralization reaction is –56 kJ/mol H2O
Ans
Trong 25,0 mL HCl 1,045M, số lượng mol H+ là:
1L 0,1045 mol 1 mol H +
25 mL . . . = 0,00261 mol H+
1000 mL L 1 mol HCl
Lượng nhiệt tỏa ra của quá trình trung hòa này là
−56 kJ. mol−1 . 0,00261 mol. (−1) = 0,15kJ
Q.15 (EX7-8A) What is the enthalpy change when a cube of ice 2.00 cm on edge is brought from –10.0 °C
to a final temperature of 23.2 °C? For ice, use a density of 0.917 g/cm3 a specific heat of 2,01 J/g–1 oC –1,
and an enthalpy of fusion of 6,01 kJ/mol.
Ans
7,336
∆H = ∆H1 + ∆H2 + ∆H3 = 23 .0,917.10-2+ . 6,01+10-3.7,336.4,18.23,2=3,31 kJ
18,015
Q.16 (EX7-8B) What is the maximum mass of ice at –15,0 oC that can be completely converted to water
vapor at 25 oC if the available heat for this transition is 5,00×103 kJ,? (heat of water evaporization at 25oC is
44 x 103 J/mol).
Ans
∆H = ∆H1 + ∆H2 + ∆H3 + ∆H4
m m
⇔ 5.106 = m. 2,01.15 + m. 4,18.25 + . 6,01.103 + . 44.103
18,015 18,015
⇒ m = 1717,8g =1,72 kg
Q.17 (EX7-9A) The standard heat of combustion of propene, C3H6(g), is –2058 kJ/mol, and C3H8(g),
is -2219 kJ/mol . Use this value and the standard enthalpy of formation of CO 2(g) and water(l) to
determine ΔHo for the hydrogenation of propene to propane.
Ans
9
C3 H6 + O2 → 3CO2 + 3H2 O ∆H = 20,1kJ. mol−1
2
C3 H8 + 5O2 → 3CO2 + 4H2 O ∆H = −104,7. kJ. mol−1
C3 H6 + H2 → C3 H8 ∆H° = −104,7 − 20,1 = −124,8kJ
Q.18 (EX7-9B) From the data in Practice Example 17 and the following equation, determine the standard
enthalpy of combustion of one mole of 2-propanol, CH3CH(O)CH3(l).
Ans
°
0,62. ∆HC° 3H8 + 0,38. ∆HC° 4 H10 kJ
∆Hhh = = −2,5.103 .
1 mol hỗn hợp
𝐐. 𝟐𝟑 (EX7-12A) The overall reaction that occurs in photosynthesis in plants is:
6 CO2(g) + 6 H2O(l) → C6H12O6(s) + 6 O2(g) ΔHo = 2803 kJ
Use this value and the standard enthalpy of formation of CO2(g) and water(l) from Appendix to determine
the standard enthalpy of formation of glucose, C6H12O6(s) at 298 K
Ans
∆HC6 H12O6 = 2803 + [6. (−393,5) + 6. (−285,8)] = −1272,8 kJ
𝐐. 𝟐𝟒 (EX7-12B) A handbook lists the standard enthalpy of combustion of gaseous dimethyl ether at 298 K
as – 31,70 kJ/g (CH3)2O (g). What is the standard molar enthalpy of formation of dimethyl ether at 298 K?
Use this value and the standard enthalpy of formation of CO2(g) and water (l) from Appendix.
Ans
(CH3 )2 O (g) + 3O2 (g) → 2CO2 (g) + 3H2 O(l) ∆H ° = −1460,419 kJ
∆H ° = {2 mol CO2 . ∆Ht° [CO2 (g)] + 3 mol H2 O . ∆Ht° [H2 O(l)]}
− {1 mol (CH3 )2 O . ∆Ht° [(CH3 )2 O (g)] − 3mol O2 [O2 (g)]}
−393,5 kJ −285,8 kJ
−1460,19kJ = 2 mol CO2 . + 3 mol H2 O . − 1 mol ∆Ht° [(CH3 )2 O (g)]
mol CO2 mol H2 O
0 kJ
− 1 mol (CH3 )2 O . −3 mol O2 .
mol O2
⇒ ∆Ht° [(CH3 )2 O (g)] = −184 kJ/mol
𝐐. 𝟐𝟓 (E9) A 74.8 g sample of copper at 143,2 oC is added to an insulated vessel containing 165 mL of
glycerol, (C3H8O3, d=1,26 g/mL), at 24,8 oC. The final temperature is 31,1 oC. The specific heat of copper is
0,385 J.g−1 . oC −1 . What is the heat capacity of glycerol in J.g−1 . oC −1?
Ans
0,385 J
qcopper = 74,8 g. . (31,1 − 143,2)℃ = −3228,3 J
g. ℃
qcopper = −qglyxerol = 3228,3 J
3228,3J
Cglyxerol = = 2,465. J. g −1 . ℃−1
165.1,26. (31,1 − 24,8)
or Cglyxerol = 2,3.102 J. mol−1 . ℃
𝐐. 𝟐𝟔 (E22) The heat of solution of KI(s) in water is 20,3 kJ/mol KI. If a quantity of KI is added to sufficient
water at 23,5 oC in a Styrofoam cup to produce 150.0 mL of 2.50 M KI, what will be the final temperature?
(Assume a density of 1.30 g/mL and a specific heat of 2,7 J.g−1 . oC −1 for 2.50 M KI.)
Ans
20,3 0,122kJ
∆H = = = 122,3J/g
166 g
KI added to prepare 150mL of 2.50 M KI
So,
2,5.150
mKI = . 166 = 62,25g
1000
Heat absorbed(q) = 62,25.122,3 = 7613,175J
We have,
Mass of solution = Volume . density = 150.1,3 = 195g
Now,
Heat for solution = m. C. ∆t
7613,175 = 195.2,7. (23,5 − t final ) → t final = 9℃
𝐐. 𝟐𝟕 (E26) The heat of neutralization of HCl(aq) by NaOH(aq) is −55,84 kJ/mol H2O produced. If 50,00
mL of 1.05 M NaOH is added to 25.00 mL of 1.86 M HCl, with both solutions originally at 24.72 oC what
will be the final solution temperature? (Assume that no heat is lost to the surrounding air and that the solution
produced in the neutralization reaction has a density of 1.02 g/mL and a specific heat of 3.98 Jg−1 oC −1)
Ans
nOH− = 0,0525 mol; nH+ = 0,0465 mol
qneutr = −qcal
−55,84.103 . 0,0465 = −75.1,02.3,98. (t final − 24,72)
⇒ t final = 33,25℃
𝐐. 𝟐𝟖 (E33) The enthalpy of sublimation for dry ice (i.e., CO2) is ΔHo= 571 kJ/kg at −78,5 oC and 1 atm. If
125.0 J of heat is transferred to a block of dry ice that is −78,5 oC, what volume of CO2 gas (d = 1.98 g/L)
will be generated?
Ans
1000J
Enthalpy of sublimation dry ice is ΔHᵒsub = 571 kJ.kg-1 = 571. = 571 J/g
1000g
⇒ Cvàng = 3,072 J. g −1 . K −1
Vậy nhiệt dung của nhiệt lượng kế không bằng nhiệt dung riêng của vàng nguyên chất
(0,1291 J. g −1 . K −1 ) nên chiếc nhẫn vàng không nguyên chất
𝐐. 𝟑𝟎 (E51) In each of the following processes, is any work done when the reaction is carried out at constant
pressure in a vessel open to the atmosphere? If so, is work done by the reacting system or on it?
(a) Neutralization of Ba(OH)2 by HCl(aq);
(b) conversion of gaseous nitrogen dioxide to gaseous dinitrogen tetroxide;
(c) decomposition of calcium carbonate to calcium oxide and carbon dioxide gas.
Ans
(a) Ba(OH)2 (aq) + HCl(aq) → BaCl(aq) + H2 O(l)
∆ng = 0 → W = 0. Công bằng không.
𝐐. 𝟑𝟏 (E137) Write the balanced chemical equations for reactions that have the following as their standard
enthalpy changes.
a. ∆Hf° = 82,05 kJ/mol N2O (k)
b. ∆Hf° = −394,1 kJ/mol SO2Cl2 (l)
°
c. ∆Hcomb = −1527 kJ/mol CH3CH2COOH (l)
Ans
1
(a) N2 (g) + O2 (g) → N2 O(g) ∆Hf° = −394,1 kJ/mol
2
(b) SO2 (g) + Cl2 (g) → SO2 Cl2 ∆Hf° = −394,1 kJ/mol
°
(c) 3C(s, graphite) + 3H2 (g) + O2 (g) → CH3 CH2 COOH(l) ∆Hcomb = −1527 kJ/mol
𝐐. 𝟑𝟐 (E70) Given the following information:
1 3
N2 (k) + H2 (k)→ NH3(k) ∆H1° = −46.2 kJ (1)
2 2
5 3
NH3 (k) + O 2 (k) → NO (k) + H2O (l) ∆H2° = −292.3 kJ (2)
4 2
1
H2 (k) + O2 (k)→H2O (l) ∆H3° = −285.8 kJ (3)
2
Determine ∆H° for the following reaction: N2 (k) + O2 (k) →2 NO (k), expressed in term of ∆H1° , ∆H2° and
∆H3° .
Ans
2.(1) N2 (k) + 3H2 (k)→ 2NH3(k) ∆H1° = −92.4 kJ
+ 5
2.(2) 2NH3 (k) + O 2 (k) →2 NO (k) + 3 H2O ∆H2° = −584.6 kJ
2
+
3
-3.(3) 3H2O (l)→ 3H2 (k) + O2 (k) ∆H3° = 857.4 kJ
2
°
2. (−348) + 2. (−296,8) + 878,2
∆𝐻𝑍𝑛𝑆 = = −206 𝑘𝐽. 𝑚𝑜𝑙 −1
2
𝐐. 𝟑𝟓 (E91) The decomposition of limestone, CaCO3 (s), into quicklime, CaO(s), and CO2 (g) is carried out
in a gas-fired kiln. Use data from Appendix D to determine how much heat is required to decompose 1,35×103
kg CaCO3(s). (Assume that heats of reaction are the same as at and 1 bar.)
Ans
CaCO3 (s) → CaO (s) + CO2 (g)
-1206,9 -636,6 -383,5
°
∆Hrxn = 178 kJ. mol−1
1.35.103 .178
So, heat 1,35×103 kg CaCO3(s) require = 2,4.106 kJ
0,1
(Explain: 1 mole require 178 kJ so 0,1 kg require 178 kJ. Therefore, heat 1,35×103 kg CaCO3(s) require
1,35.103 .178
)
0,1
𝐐. 𝟑𝟔 (E95) A British thermal unit (Btu) is defined as the quantity of heat required to change the temperature
of 1 lb of water by 1 o F. Assume the specific heat of water to be independent of temperature. How much heat
is required to raise the temperature of the water in a 40 gal water heater from 48 to 145 °F in
(a) Btu?
(b) kcal?
(c) kJ?
Ans
Volume = 40 gal=40.4,55.103 = 181,8.103 mL
Mass water = density . volume = 1. 181,8.103 = 182.103 gam
5
Intital temperature (Ti) = (48-32)=8,89℃
9
5
Final temperature (Tf) = . (145 − 32) = 62,78℃
9
∆T = 53,89℃ → q = 41027.103 J
(a) 1Btu = 1055.05 → q = 38,89.103 Btu
1
(b) q = 41027.103. = 9805,6 Kal
4,184.103
(c) q = 41027 kJ
𝐐. 𝟑𝟕 (E130) The temperature increase of 225 mL of water at 25 oC contained in a Styrofoam cup is noted
when a 125 g ample of a metal at 75 oC is added. With reference to 7 Appendix, the greatest temperature
increase will be noted if the metal is (a) lead; (b) aluminum; (c) iron; (d) copper.
Ans
So, we can calculating it
C. J
qmetal = 125g. . (t − 75)℃ = 125. C. (t sys − 75)J
g. ℃ sys
4,18J
qwater = 225g. (t − 25)℃ = 940,5. C. (t sys − 25)J
g. ℃ sys
Conservation of energy:
qmetal = −qwater ⇒ 125. C. (t sys − 75) = −940,5. C. (t sys − 25)
For each metal at (a), (b), (c), (d) → 25,85℃ ; 30,23℃ ; 27,82℃ ; 27,43℃
Therefore, the greatest temperature increase will be noted if the metal is aluminum
𝐐. 𝟑𝟖 (E101) A particular natural gas consists, in mole percents, of 83.0% CH4, 11.2% C2H6 and 5.8% C3H8.
A 385 L sample of this gas, measured at 22.6 oC and 739 mmHg, is burned at constant pressure in an excess
of oxygen gas. How much heat, in kilojoules, is evolved in the combustion reaction?
Ans
Combustion of methane takes place as:
CH4(g) +2O2(g) → CO2(g )+ 2H2O
°
ΔHcombustion of methane = −802.31 kJ/mol
Now we calculate the energy produced by the combustion of each gas and the total energy produced
°
𝐪𝐂𝐇𝟒 = 𝐧𝐂𝐇𝟒 . (−𝚫𝐇𝐜𝐨𝐦𝐛𝐮𝐬𝐭𝐢𝐨𝐧 𝐨𝐟 𝐦𝐞𝐭𝐡𝐚𝐧𝐞 ) = 𝟏𝟎, 𝟐𝟗𝐤𝐉
°
𝐪𝐂𝟐 𝐇𝟔 = 𝐧𝐂𝟐 𝐇𝟔 . (−𝚫𝐇𝐜𝐨𝐦𝐛𝐮𝐬𝐭𝐢𝐨𝐧 𝐨𝐟 𝐞𝐭𝐡𝐚𝐧𝐞 )= 𝟐, 𝟒𝟕 𝐤𝐉
°
𝐪𝐂𝟑 𝐇𝟖 = 𝐧𝐂𝟑 𝐇𝟖 . (−𝚫𝐇𝐜𝐨𝐦𝐛𝐮𝐬𝐭𝐢𝐨𝐧 𝐨𝐟 𝐩𝐫𝐨𝐩𝐚𝐧𝐞 ) = 𝟏, 𝟖𝟑𝐤𝐉
Ans
(a) Nhiệt toả ra các sản phẩm được tạo thành và tăng dần cho tới khi ở cân bằng hoá học, tại đó nhiệt
độ là lớn nhất nhưng sau đó sau khi trung hoà hoàn toàn và dư thừa các chất tham gia thì nhiệt độ
giảm do một phần các chất tham gia phản ứng dư thừa đó sẽ hấp thu nhiệt.
(b) Axit cỉtric có thể cho 3 proton nên
H3 C6 H5 O7 (s) + 3Na+ (aq) + 3OH − (aq) → 3H2 O (l) + 3Na+ (aq) + C6 H5 O3−
7 (aq)
B.
a. Zn(r) + Ag2O(r) → ZnO(r) + 2 Ag(r)
Can not predict for this reaction
b. 2 Cl– (dd) + 2 H2O(l) → 2 OH– (dd) + Cl2(k) + H2(k)
∆ng = 2 → ∆S ° increases
𝐐. 𝟐 (EX 19.2) A. What is the standard molar entropy of vaporization, for a chlorofluorocarbon that once
was heavily used in refrigeration systems? Its normal boiling point is −29,79 o C and ∆H°vap = 20.2 kJ.mol–1
Ans
° ∆H°vap 20,2.103
∆Svap = = = 83,04 J. mol−1 . K −1
T −29,79+273,15
𝐐. 𝟑 (EX 19.2) B. The entropy change for the transition from solid rhombic sulfur to solid monoclinic sulfur
at 95.5 o C is ∆Sotr = 1,09 J.mol−1 K −1 . What is the standard molar enthalpy change, ∆Ho tr, for this transition
Ans
°
∆Htr = 1,09. (95,5 + 273,15) = 402 J. mol−1
𝐐. 𝟒 (EX 19.3) A. Use data from Appendix D to calculate the standard molar entropy change for the
°
synthesis of ammonia from its elements. N2(g) + 3 H2(g) → 2 NH3(g) ∆S298K =?
Ans
1 3
N2(g) + H2(g) → NH3(g)
2 2
° °
∆S ° = ∆S(product) − ∆S(reactant)
1 3
= 1 mol. S ° [NH3 (g)] − mol S ° [N2 (g)] − . mol. S ° [H2 (g)]
2 2
J 1 J 3 J
= 1 mol. 192,5 . − mol. 191,6. − mol. 130,7.
mol.K 2 mol.K 2 mol.K
= −99,35. J. K −1
𝐐. 𝟓 (EX 19.3) B. N2O3 is an unstable oxide that readily decomposes. The decomposition of 1.00 mol of to
nitrogen monoxide and nitrogen dioxide at is accompanied by the entropy change ∆S° = 138.5 J K-1 . What
is the standard molar entropy of at 25 °C?
Ans
°
N2O3(g) → NO(g) + NO2(g) ∆S298K = 138,5 J.K
∆SN° 2O3 = 210,8 + 240,1 − 138,5 = 312,4 J. mol−1 . K −1
𝐐. 𝟔 (EX 19.4) A. Which of the four cases in Table 19.1 would apply to each of the following reactions:
°
(a) N2(g) + 3 H2(g) → 2 NH3(g) ∆H298K = −92,22 kJ
°
(b) 2 C(graphite) + 2 H2(g) → C2H4(g) ∆H298K = 52,26 KJ
Ans
(a) ∆ng = −2 → ∆S ° < 0 and ∆H° < 0 → Xảy ra ở điều kiện thường
(b) ∆ng = −1 → ∆S ° < 0 and ∆H° > 0 → Không xảy ra ở điều kiện thường
𝐐. 𝟕 (EX 19.4) B. Under what temperature conditions would the following reactions occur spontaneously?
(a) The decomposition of calcium carbonate into calcium oxide and carbon dioxide. (b) The roasting of zinc
sulfide in oxygen to form zinc oxide and sulfur dioxide. This exothermic reaction releases 439.1 kJ for every
mole of zinc sulfide that reacts
Ans
(a) Xảy ra ở nhiệt độ cực lớn
(b) Xảy ta ở nhiệt độ thấp
°
𝐐. 𝟖 (EX 19.5) A. Determine ∆Go at 298.15 K for the reaction 4 Fe(r) + 3 O2(k) → 2 Fe2O3(r) ∆H298K =
−1648 kJ and ∆So 298K = −549.3 J K−1
Ans
∆G = ∆H − T. ∆S = −1484,3 kJ
𝐐. 𝟗 (EX 19.5) B. Determine for the reaction in Example 19–5 by using data from Appendix D.
°
Compare the two results. 2 NO (g) + O2 (g) → 2 NO2 (g) ∆G298K =?
Ans
° °
∆G° = ∆G(product) − ∆G(reactant)
= 2. mol. ∆Gf° [ NO2 (g)] − 2. mol. ∆Gf° [NO (g)] − 1. mol. ∆Gf° [O2 (g)]
kJ kJ kJ
= 2 mol. 51,31. − 2 mol. 86,55. − 1 mol. 0
mol mol mol
= -70,48 kJ.
𝐐. 𝟏𝟎 (EX 19.7)
A. Use the data in Appendix D to decide whether the following reaction is spontaneous under standard
conditions at 298.15 K. N2O4(g) → 2 NO2(g)
B. If a gaseous mixture of and both at a pressure of 0.5 bar, is introduced into a previously evacuated vessel,
which of the two gases will spontaneously convert into the other at 298.15 K.
Ans
A. ∆G° = 4,73. kJ. mol−1 > 0 → Không xảy ra ở nhiệt độ 298K
B. Q P = 0,5 > K P = 0,148 → theo chiều nghịch
𝐐. 𝟏𝟏 ❖ (EX 19.8) A. Determine the equilibrium constant at 298.15 K for AgI(s) Ag+ (aq) + I− (aq)
Compare your answer to the for AgI in Appendix D.
Ans
AgI(s) Ag+(aq) + I-(aq)
At 298 K
∆H° = 112250J
∆S ° = 68,31. J. K −1
∆G° = ∆H° − T∆S ° ⇔ −RTlnK = ∆H° − T∆S °
⇒ − 2,303.8,314.298,15. logK = 91883,37 ⇒ K = 8,13.106−17
𝐐. 𝟏𝟐 (EX 19.8) B. At 298.15 K, should manganese dioxide react to an appreciable extent with 1 M HCl(aq),
producing manganese(II) ion in solution and chlorine gas?
Ans
MnO2 (s) + 5H + (aq) + 2Cl− (aq) → Mn2+ (aq) + Cl2 (g) + 2H2 O(l)
∆G° = -228.1 kJ +0.0 kJ +2.(-237.1 kJ) - (-465.1 kJ)-4. 0.0 kJ – 2. (-131.2 kJ) = +25.2 kJ > 0, phản ứng không
xảy ra
𝐐. 𝟏𝟑 ❖ (EX 19.9) A. At what temperature will the formation of NO (g) from NO(g) and O2(g) have Kp =
⎯⎯
1.50×102 ? For the reaction 2 NO(g) + Cl2(g) ⎯
⎯→ 2 NOCl(g) at 25 o C, ∆Ho = −114,1 kJ.mol−1 và ∆So =
−146,5 J.mol−1 .K−1
Ans
∆𝐻 °
∆𝐺 ° = ∆𝐻 ° − 𝑇∆𝑆 ° = −𝑅𝑇𝑙𝑛𝐾 → ∆𝐻 ° = 𝑇(∆𝑆 ° − 𝑅𝑙𝑛𝐾 ) → 𝑇 = = 606𝐾
∆𝑆 ° − 𝑅𝑙𝑛𝐾
𝐐. 𝟏𝟒 ❖ (EX 19.9) B. For the reaction 2 NO(g) + Cl2(g) 2 NOCl(g), what is the value of K at (a)
25oC (b) 75oC Use data from Example 19–9. [Hint: The solution to part (a) can be done somewhat
more simply than that for (b)]. (∆H ° = −114.1 kJ. mol−1 and ∆S ° = −146.5 J. mol−1 . K −1 )
Ans
1000J
∆H ° = −114,1 kJ. mol−1 . = -114100 J.mol-1
1kJ
° −1 −1
∆Sbay hơi ≈ 87 J. mol . K
°
°
∆Hbay hơi
∆Sbay hơi = → T = 305,75K
T
° °
(b) ∆G° = ∆Hbay hơi − T∆Sbay hơi = −0,25J
(c) Phản ứng luôn xảy ra ở mọi nhiệt độ và theo chiều từ trái sang phải.
𝐐. 𝟏𝟖 (E.31) Assess the feasibility of the reaction N2H4 (k) + 2 OF2 (k) N2F4 (k) + 2 H2O (k) by determining
each of the following quantities for this reaction at 25 o C
(a) ∆So (The standard molar entropy of N2F4 (g) is 301.2 J K–1 )
(b) ∆Ho (Use data from Appendix and F−O and N−F bond energies of 222 and respectively)
(c) ∆G°
Ans
(a) ∆S° = 2.188,8 + 301,2 − 238,5 − 2.247,4 = −54,5 J
(b) ∆H° = ∆D°product − ∆D°reactant = 4.389 + 4.222 − 4.301 − 4.464 = −616 kJ
𝐐. 𝟐𝟑 (E.36) Calculate the equilibrium constant and Gibbs energy for the reaction CO (k) + 2 H2 (k) →
CH3OH (k) at 483 K by using the data tables from Appendix D. Are the values determined here different
from or the same as those in exercise 35? Explain.
Ans
Ho = −200.7kJmol-1 − (−110.5kJmol-1 + 2.0kJmol-1 ) = −90.2kJmol-1
So = 239.8JK−1 mol-1 − (197.7JK−1 mol-1 + 2 130.7JK−1 mol-1 ) = −219.3JK-1mol-1
483K (−219.3)kJK−1 mol−1
Go = −90.2kJmol-1 − = 15.7kJmol-1
1000
𝐐. 𝟐𝟒 ❖ (E.41) Use thermodynamic data at 298 K to decide in which direction the reaction 2 SO 2 (g) + O2
(g) 2 SO3 (g) is spontaneous when the partial pressures of SO2, O2 and SO3 are 1,0×10–4 , 0.20, and 0.10
atm, respectively.
Ans
°
∆G298K = 2∆Gf° [ SO3 (g)] − ∆Gf° [O2 (g)] − 2∆Gf° [SO2 (g)]
= 2. mol. ∆Gf° [ SO3 (g)] − 1. mol. ∆Gf° [O2 (g)] − 2. mol. ∆Gf° [SO2 (g)]
kJ kJ kJ
= 2. mol. (−371,1) − 1. mol. 0 − 2. mol. (−300,2) = −141,6 kJ
mol mol mol
° 2
(𝑃𝑆𝑂3
) (0,1 )2
𝐾𝑃 = 2 = −4 2
. 𝑎𝑡𝑚 = 5.106 𝑎𝑡𝑚
°
(𝑃𝑆𝑂 2
) . 𝑃𝑂°2 (1,0.10 ) .0,20
°
1000J J
∆G = ∆G298K + RT. ln(K P ) = −141,6kJ. + 8,314. . 298K. ln(5.106 )
1 kJ mol. K
= −103383,6J = −103,4kJ < 0
𝐐. 𝟐𝟔 (E.86) The decomposition of the poisonous gas phosgene is represented by the equation COCl2 (g)
⎯⎯
⎯ ⎯→ CO (g) + Cl2. Values of for this reaction are Kp = 6.7×10–9 at 99.8 o C and 4.44×10–2 at 395 o C. At
what temperature is 15% dissociated when the total gas pressure is maintained at 1.00 atm?
Ans
K1 Ea 1 1
ln ( ) = .( − )
K2 R T2 T1
→ Ea = 1,1.105 J/mol
6,7.10−9
So with 15% dissociated → K p = = 1,005.10−9
0,15
6,7.10−9 Ea 1 1
Now, ln ( )= .( − ) → T2 = 353,9K
1,005.10−9 R T2 99,8+273
𝐐. 𝟐𝟕 (E.109) A handbook lists the following standard enthalpies of formation at 298 K for cyclopentane
C5H10 (l) = –105.9 kJ mol–1 , and C5H10 (k) = –77.2 kJ mol–1
a. Estimate the normal boiling point of cyclopentane.
b. Estimate for the vaporization of cyclopentane at 298 K.
c.Comment on the significance of the sign of ∆G° at 298 K
Ans
(−77,2+105,9).103
(a) Tsôi = = 330𝐾
87
⎯⎯
→ N2O (g) + 2 H2O(l) at 298 K.
𝐐. 𝟐𝟖 (E.110) Consider the reaction: NH4NO3 (s) ⎯
⎯
(a) Is the forward reaction endothermic or exothermic?
(b) What is the value of ∆Go at 298 K?
(c) What is the value of K at 298 K?
(d) Does the reaction tend to occur spontaneously at temperatures above 298 K, below 298 K, both, or neither
Ans
°
(a) ∆Hrxn = −124 kJ. Thus, the forward reaction is exothermic
°
(b) ∆Grxn = −186,1 kJ
°
(c) ∆Grxn = −RT. lnK → K = 4,127.1032
° °
(d) ∆Srxn = 209 J/K. Thus, ∆Grxn < 0 at all temperatures
so the reaction is spontaneous at all temperatures
𝐐. 𝟐𝟗 ❖ Which of the following diagrams represents an equilibrium constant closest to 1?
Ans
Sơ đồ (a). Vì với sơ đồ (a) thì ∆G° = ∆Gpro
° °
− ∆Greact ≈ 0 nhất nên do đó hằng số cân bằng gần nhất với 1
tức K≈ 1.
𝐐. 𝟑𝟎 (E.112) At room temperature and normal atmospheric pressure, is the entropy of the universe positive,
negative, or zero for the transition of carbon dioxide solid to liquid?
Ans
Carbon dioxide is a gas at room temperature. The melting point of carbon dioxide is expected to be very low.
At room temperature and normal atmospheric pressure this process is spontaneous. The entropy of the
universe is positive.
CHAPTER 3. CHEMICAL KINETICS
𝐐. 𝟏 (EX-14-1A) At some point in the reaction 2 A + B → C + D, [A] = 0.3629 M. At a time 8.25 min later
[A] = 0.3187. What is the average rate of reaction during this time interval, expressed in M.s–1?
Ans
−[A] −(0,3187M−0,3629M)
Avg rate = = 60 sec = 4,46.10−5 M. s −1
∆t.a 8,25 min. .2
1 min
𝐐. 𝟐 (EX–14-1B) In the reaction 2 A → 3 B, [A] drops from 0.5684 M to 0.5522 M in 2.50 min. What is the
average rate of formation of B during this time interval, expressed in M s–1 ?
Ans
0.5522 M−0.5684 M 3 𝑚𝑜𝑙𝑒𝑠 𝐵
rateof B formation= 𝟔𝟎𝒔 . −2 𝑚𝑜𝑙𝑒𝑠 𝐴 = 1,62.10−4 𝑀. 𝑠 −1
𝟐,𝟓 𝒎𝒊𝒏.𝒎𝒊𝒏
(Chú thích: do tìm tại t=2400s do đó kẻ trực tiếp tuyến tại t=2400s chiếu lên rồi xác định và phân đuôi phương
trình đường thẳng phải gần sát với biểu đồ cong)
(a) The rate of reaction determined from the slope of a tangent line to a concentration-time curve is
the instantaneous rate of reaction at the point where the tangent line touches the curve.
From the above graph, the two points selected on the tangent drawn (red line) at 2400 s are as follows:
Hence, instantaneous rate at 2400 s is
(b)
The instantaneous rate holds constant for the next 50 seconds i.e. from 2400 s to 2450 s.
Calculate the concentration at 2450 s using the concentration at 2400 s.
Hence,
𝐐. 𝟒 (EX-14-2B) Use data only from the following table to determine [H2O2 ] at t = 100 s. Compare this
value with the one calculated in Example 14-2(b). Explain the reason for the difference?
Ans
𝐐. 𝟓 (EX-14-3A) The decomposition of N2O5 is given by the following equation: 2 N2O5 → 4 NO2 + O2 .
At an initial [N2O5]0 = 3.15 M, the initial rate of reaction = 5.45×10 –5 M s –1 and when [N2O5]0 = 0.78 M,
the initial rate of reaction = 1.35×10 –5 M s –1 . Determine the order of this decomposition reaction.
Ans
𝐐. 𝟔 (EX-14-3B) Consider a hypothetical Experiment 4 in Table 14.3, in which the initial conditions are
[HgCl2 ]0 = 0.025 M and [C2O4 2– ]0 = 0.045, v = k [HgCl2 ]2 [C2O4 2– ]2 . Predict the initial rate of reaction.
Ans
𝐐. 𝟕 (EX-14-4A) A reaction has the rate law: v = k [A]2[B]. When [A] = 1.12 M and [B] = 0.87 M and the
rate of reaction = 4.78×10 –2 Ms -1 . What is the value of the rate constant, k?
Ans
𝐐. 𝟖 (EX-14-4B) What is the rate of reaction 2 HgCl2 + C2O42– → 2 Cl– + 2 CO2 + Hg2Cl2 , v = k [HgCl2 ]1
[C2O42– ]2 , at the point where [HgCl2 ] = 0.050 M and [C2O42– ]0 = 0.025 M
Ans
𝐐. 𝟗 (EX-14-5A) The reaction A → 2 B + C is first order. If the initial [A] = 2.80 M and k = 3.02×10 –3 s –1
, what is the value of [A] after 325 s?
Ans
𝐐. 𝟏𝟎 (EX-14-5B) Use data in the following Figure and Table, together with equation ln[A]t = -kt + ln [A]0
, to show that the decomposition of H2O2 is a first-order reaction. [Hint: Use a pair of data points for H2O20
and H2O2t and their corresponding times to solve for k. Repeat this calculation using other sets of data. How
should the results compare?]
Ans
𝐐. 𝟏𝟐 (EX-14-6B) At what time after the start of the reaction is a sample of [H2O2 ] two–thirds decomposed?
Ans
𝐐. 𝟏𝟑 (EX-14-7A) Di-t-butyl peroxide (DTBP) is used as a catalyst in the manufacture of polymers. In the
gaseous state, DTBP decomposes into acetone and ethane by a firstorder reaction.
Start with DTBP at a pressure of 800.0 mmHg at 147 °C. What will be the pressure of DTBP at t = 125
min, if t1/2 = 8,0×10 –1 min. [Hint: Because 125 min is not an exact multiple of the half-life, you must use
ln(𝑃𝐴 )𝑡
equation (𝑃𝐴 )0
= −𝑘𝑡. Can you see that the answer is between 200 and 400 mmHg?]
Ans
𝐐. 𝟏𝟒 (EX-14-7B) Use data from Table 14.4 to determine (a) the partial pressure of ethylene oxide, and (b)
the total gas pressure after 30.0 h in a reaction vessel at 415 °C, if the initial partial pressure of (CH2)2O is
782 mmHg.
Ans
Ans
𝐐. 𝟏𝟓 (EX-14-8A) In the decomposition reaction B → products, the following data are obtained.
What are the order of this reaction and its rate constant k?
Ans
Try in zero order equation:
0,88M − 0,74M
t = 25 → k 0 = = 5,6.10−3 M. s −1
25s
0,88M − 0,62M
t = 50 → k1 = = 5,2.10−3 M. s −1
50s
0,88M − 0,52M
t = 75 → k 2 = = 4,8.10−3 . M. s −1
75
Try in first order equation:
2,303 0,88
t = 25 → k 0 = . log ( ) = 6,9321.10−3 M. s −1
25 0,74
2,303 0,88
t = 50 → k 0 = . log ( ) = 7,0053.10−3 M. s −1
50 0,62
2,303 0,88
t = 75 → k 0 = . log ( ) = 7,0158.10−3 M. s −1
75 0,52
2,303 0,88
t = 100 → k 0 = . log ( ) = 6,9327.10−3 M. s −1
100 0,44
2,303 0,88
t = 150 → k 0 = . log ( ) = 6,9569.10−3 M. s −1
150 0,31
2,303 0,88
t = 200 → k 0 = . log ( ) = 6,9327.10−3 M. s −1
200 0,22
2,303 0,88
t = 250 → k 0 = . log ( ) = 6,8202.10−3 M. s −1
250 0,16
As rate constant at all "t" values are constant
→ The order equation this reaction is first and average rate constant (k) = 6,9422.10-3.M.s-1
𝐐. 𝟏𝟔 (EX-14-8B) The following data are obtained for the reaction A → P. What are the order of this reaction
and its rate constant, k?
Ans
𝐐. 𝟏𝟕 (EX-14-9A) What is the half-life of the first-order decomposition of N2O5 at 75.0 °C? With Ea
=1,06×105 J/mol and k = 3,46×10–5 s –1 at 298 K
Ans
𝐐. 𝟏𝟖 (EX-14-9B) At what temperature will it take 1.50 h for two-thirds of a sample of N2O5 in to decompose
in Example 17.[ The first-order decomposition of N2O5 , Ea =1,06×105 J/mol and k = 3,46×10–5 s –1 at 298 K
]
Ans
[N2 𝑂5 ]𝑡 1
𝑙𝑛 = ln ( ) = −𝑘. 1,5.3600 → 𝑘 = 2,03.10−4 𝑠 −1
[𝑁2 𝑂5 ]0 3
The Arrhenius equation :
2,03.10−4 1,06 × 105 𝐽. 𝑚𝑜𝑙 −1 1 1
ln ( ) = . ( − ) → 𝑇2 = 311𝐾
3,26.10−5 8,314𝐽. 𝑚𝑜𝑙−1 . 𝐾 −1 298𝐾 𝑇2
𝐐. 𝟏𝟗 (EX-14-10A) In a proposed two-step mechanism for the reaction CO(g) + NO2 (g) → CO2 (g) +
NO(g), the second, fast step is NO3 (k) + CO(k) → CO2 (k) + NO2 (k). What must be the slow step? What
would you expect the rate law of the reaction to be? Explain
Ans
𝐐. 𝟐𝟐 (E10) At the half-life for the first-order decomposition of N2O5(g) is 2.38 min. N2O5(g) → 2 NO2(g)
+ 1/2 O2(g) If 1.00 g of N2O5(g) is introduced into an evacuated 15 L flask at 65 °C,
(a) What is the initial partial pressure, in mmHg, of N2O5(g)?
(b) What is the partial pressure, in mmHg, of N2O5(g) after 2.38 min?
(c) What is the total gas pressure, in mmHg, after 2.38 min?
Ans
1
nRT mol.0,0821.L.atm.mol−1 .K−1 .338,15K 760 mmHg
108,009
(a) P0 = = . =13,023mmHg
V 15L 1 atm
ln2 ln2
(b) Bậc 1: K = = = 0,2912 min−1
𝑡1/2 2,38
=22,7895mmHg
𝐐. 𝟐𝟑 (E20) In the first-order reaction A → products, A = 0.816 M initially and 0.632 M after 16.0 min.
(a) What is the value of the rate constant, k?
(b) What is the half-life of this reaction?
(c) At what time will A = 0.235 M?
(d) What will A be after 2.5 h?
Ans
(a) In first order equation
1 [A]0 1 0,816
k= ln. = . ln ( ) = 0,016. min−1
t [A]t 16 0,632
ln2 ln2
(b) t 1 = = = 43,42 min
2 k 0,016
1 [A] 1 0,816
(c) t = ln. [A]0 = . ln ( ) = 77,8 min
k t 0,016 0,235
0,01
ln ( ) = −0,048. t → t = 96 days
1
𝐐. 𝟐𝟓 (E23) Acetoacetic acid, CH3COCH2COOH, a reagent used in organic synthesis, decomposes in acidic
solution, producing acetone and CO2(g).
CH3COCH2COOH(aq) → CH3COCH3(aq) + CO2(g)
This first-order decomposition has a half-life of 144 min.
(a) How long will it take for a sample of acetoacetic acid to be 65% decomposed?
(b) How many liters of CO2(g), measured at 24.5 °C and 748 Torr, are produced as a 10.0 g sample of
CH3COCH2COOH decomposes for 575 min? [Ignore the aqueous solubility of CO2(g).
Ans
ln2
(a) k = = 4,81.10−3 min−1
144
0,35. [A]0
ln ( ) = −kt → t = 218 min
[A]0
10
(b) nacetoacetic aci= = 0,09795 moles
102,09
[A]t
ln ( ) = −kt = −4,81.10−3 . 575 = −2,766 → [A]t = 6,16.10−3 moles
[A]0
[A]reacted=0,09179 moles
nRT 0,09179.0,082.297,65
VCO2 = = = 2,3 L CO2
P 1
748.
760
𝐐. 𝟐𝟕 (E36) For the disproportionation of p-toluenesulfinic acid 3ArSO2H → ArSO2Ar + ArSO3H + H2O
(where Ar = p-CH3C6H4–), the following data were obtained
(a) Show that this reaction is second order.
(b) What is the value of the rate constant, k?
(c) At what time would ArSO2H = 0.0500 M
(d) At what time would ArSO2H = 0.2500 M
(e) At what time would ArSO2H = 0.0350 M
Ans
(a)
1 1
(c) [A] = kt + [A] → 𝑡 = 73 𝑚𝑖𝑛
t 0
1 1
(d) [A] = kt + [A] → 𝑡 = 219 𝑚𝑖𝑛
t 0
1 1
(e) [A] = kt + [A] → 𝑡 = 136 𝑚𝑖𝑛
t 0
𝐐. 𝟐𝟗 (E41) In three different experiments, the following results were obtained for the reaction A →
products: A0 = 1.00 M, t1/2 = 50 min; A0 = 2.00 M, t1/2 = 25 min; A0 = 0.50 M, t1/2 = 100 min. Write the
rate equation for this reaction, and indicate the value of k?
Ans
1
t1/2 ∝
[A]0 n−1
50 1 1−n
Ở thí nghiệm (1) và (2) nồng độ tăng 2 lần thì chu kỳ bán rã giảm 2 lần nên =( )
25 2
→ n = 2. Vì vậy đây là phản ứng bậc 2.
1 1 1
Do đó, t1/2= →k= = = 0,02. M −1 . min−1
k.[A]0 t1/2 .[A]0 1M.50min
𝐐. 𝟏
Ans
1/2
[Cu+ ]2 [Sn4+ ] 2+ ]
x3 x
K= → [ Cu = ( ) = M
[Cu2+ ]2 [Sn2+ ] Kx 1,22
𝐐. 𝟖 (EX-15-4B) The steam–iron process is used to generate mostly for use in hydrogenating oils. Iron metal
and steam react [H2O(g)] to produce Fe3O4(s) và H2(g). Write expressions for KC and for KP this reversible
reaction. How are the values of KC and KP related to each other? Explain.
Ans
⎯⎯
→ Fe3 O4 (s) + 4H2 (g)
4Fe(s) + 4H2 O(g) ⎯
⎯
4
(PH2 ) [H ]4
Kp = 4 = 1; K c = [H 2 4; Vì ∆ng = 0. Vì vậy, K p = K c .
(PH2O ) 2 O]
𝐐. 𝟏𝟓 (EX-15-8A) The reaction N2O4(g) ⎯ ⎯⎯ → 2 NO2(g) has ∆Ho = +57.2 kJ. Will the amount of NO2(g)
⎯
formed from be greater at high or low temperatures?
Ans
Phản ứng trên là phản ứng thu nhiệt nên muốn tạo ra nhiều sản phẩm NO2(g) phải thực hiện phản ứng ở nhiệt
độ cao để phản ứng dịch theo chiều thuận tạo ra được nhiều NO2(g) hơn.
𝐐. 𝟐𝟏 (EX-15-11A) Sodium hydrogen carbonate (baking soda) decomposes at elevated temperatures and is
one of the sources of when this compound is used in baking. 2 NaHCO3(s) ⎯⎯⎯ ⎯→ Na2CO3(s) + H2O(g) +
CO2(g); Kp = 0.231 at 100 °C What is the partial pressure of when this equilibrium is established starting
with NaHCO3(s).
Ans
⎯⎯
→ NH3(g) + H2S(g); Kp = 0.108 at 25 oC
NH4HS(s) ⎯
⎯
(a) A sample of NH4HS(g) is introduced into an evacuated flask at. What is the total gas pressure at
equilibrium?
(b) If enough additional NH3(g) is added to the flask to raise its partial pressure to 0.500 bar at equilibrium,
what will be the total gas pressure when equilibrium is reestablished?
Ans
(a) K p = pNH3 . pH2S → pNH3 = pH2S = 0,328633 bar → Ptotal = 0,657 bar
0,108
(b) K p = 0,108 = pH2 S . pNH3 → pH2 S = = 0,216 bar → Ptotal = 0,216 + 0,5 = 0,716 bar
0,5
1,4
½ N2(g) + ½ O2(g) + ½ Br2(g) ⇌ NOBr(g) Kc = = 9,66.10−16
√2,1.1030
𝐐. 𝟑𝟔 (E57) Explain how each of the following affects the amount H2 of present in an equilibrium mixture
in the reaction
3 Fe(s) + 4 H2O(g) ⇌ Fe3O4(s) + 4 H2(g); ∆rH° = –150 kJ mol–1 .
(a) Raising the temperature of the mixture
(b) Introducing more
(c) Doubling the volume of the container holding the mixture
(d) Adding an appropriate catalyst.
Ans
3 Fe(s) + 4 H2O(g) ⇌ Fe3O4(s) + 4 H2(g); ∆rH° = –150 kJ mol–1 .
(a) Phản ứng này là phản ứng toả nhiệt với ∆rH° = –150 kJ mol–1< 0. Do đó, tăng nhiệt độ lên cao sẽ có lợi
cho phản ứng nghịch (phản ứng thu nhiệt). Nên lượng H2(g) ở nhiệt độ cao sẽ ít hơn lượng H2(g) ở nhiệt
độ thấp.
(b) H2O (g) là một trong các chất tham gia phản ứng. Do đó, khi thêm vào nhiều hơn sẽ chuyển dịch cân
bằng về bên phải (chiều thuận) để chống lại sự tăng lên của H2O (g). Nên dẫn đến tăng lượng khí H2(g).
(c) ∆𝑛𝑔 = 4 − 4 = 0. Nên sự thay đổi của thể tích bình chứa không ảnh hưởng đến cân bằng. Do đó lượng
H2(g) không bị ảnh hưởng
(d) Chất xúc tác chỉ làm tăng tốc độ phản ứng đạt đến vị trí cân bằng và không làm thay đổi nồng độ cân
bằng. Nên việc thêm một chất xúc tác thích hợp không ảnh đến lượng H2 (g) ở trạng thái cân bằng.
CHAPTER 5. ACIDS-BASE
𝐐. 𝟏 (EX 16-1A) A. For each of the following reactions, identify the acids and bases in both the forward
and reverse directions
a. HF + H2O = F– + H3O+
b. HSO4 – + NH3 = SO4 2– + NH4+
c. CH3COO– + HCl = CH3COOH + Cl–
Ans
𝐐. 𝟐 (EX 16-1B) Of the following species, one is acidic, one is basic, and one is amphiprotic in their reactions with
water: HNO2, PO4 3– , HCO3 – . Write the four equations needed to represent these facts
Ans
𝐐. 𝟑 (EX 16-2A) Students found that a yogurt sample had a pH of 2.85. What are the [H+] and [OH– ] of the
yogurt?
Ans
[H3O+] = 10-pH = 1,41.10-3
pH + pOH = 14 → pOH = 11,15→[OH] = 10-pOH = 7,01.10-12
𝐐. 𝟒 (EX 16-2B) The pH of a solution of HCl in water is found to be 2.50. What volume of water would you add to
1.00 L of this solution to raise the pH to 3,10.
Ans
[H3O+](trước) = 10-2,5=3,16.10-3 M → 𝑛𝐻3𝑂+ = 3,16.10−3 mol
3,16.10−3
[H3O+] (sau) = 10-3,1=7,94.10-4 M → 𝑉 = =4𝐿
7,94.10−4
Vthêm = 4 L - 1 L =3 L
𝐐. 𝟓 (EX 16-3A) 0.0025 M solution of HI(aq) has Calculate and the pH of the solution.
Ans
HI là axit mạnh nên phân ly hoàn toàn. Vì vậy, [H3O+]=[I-]=0,0025 M
pOH = 14 – pH = 14 – [-log(0,0025)] = 11,4 → [OH] = 10−𝑝𝑂𝐻 = 10−11,4 = 4.10−12 M
𝐐. 𝟔 (EX 16-3B). If 535 mL of gaseous HCl, at and 747 mmHg, is dissolved in enough water to prepare 625 mL of
solution, what is the pH of this solution?
Ans
1 𝑎𝑡𝑚 1𝐿
(747 𝑚𝑚𝐻𝑔 . ). 535 𝑚𝐿 .
760 𝑚𝑚𝐻𝑔 1000 𝑚𝐿
Amount mol HCl ? = = 0,021 𝑚𝑜𝑙 𝐻𝐶𝑙
0,0821 𝑎𝑡𝑚.𝐿.𝑚𝑜𝑙 −1 .𝐾 −1 .(26,5+273)𝐾
pH = -log(0,021)=1,67
𝐐. 𝟕 (EX 16-4A) Milk of magnesia is a saturated solution of Its solubility is 9.63 mg Mg(OH)2/100.0 mL
solution at 20 oC. What is the pH of saturated at Mg(OH)2 at 20 oC.
Ans
9,63.10−3 1
[OH-] = . . 2=0,0033 M
100.10−3 58,32
→ 𝑝𝐻 = 14 − (− log(0,0033) = 11,52
𝐐. 𝟖 (EX 16-4B) Calculate the pH of an aqueous solution that is 3.00% KOH, by mass, and has a density of
1.0242g/mL.
Ans
𝐐. 𝟗 (EX 16-5A) Hypochlorous acid, HOCl, is used in water treatment and as a disinfectant in swimming pools. A
0.150 M solution of HOCl has a pH of 4.18. Determine for hypochlorous acid.
Ans
[H3O+] = 10-4,18 = 6,61.10-5 M
𝐐. 𝟏𝟎 (EX 16-5B) The much-abused drug cocaine is an alkaloid. Alkaloids are noted for their bitter taste, an indication
of their basic properties. Cocaine is soluble in water to the extent of solution, and a saturated solution has a. What is
the value of for cocaine?
Dịch:
Cocain (chiết xuất từ là coca, là một loại ma tuý bị lạm dụng nhiều nhất hiện nay và bị cấm tang trữ, mua bán, vận
chuyển, sử dụng trái phép trên thế giới do gây nghiện và hoang tưởng) là một alkaloid có vị đắng đặc trưng. Biết rằng
cocain, C17H21O4N, có độ tan lên đến 0,17 g/ 100 mL dung dịch và dung dịch cocain bão hoà có pH= 10,8, tính Kb của
cocain.
Ans
pOH = 14 – 10,8 = 3,2 → [𝑂𝐻 − ] = 6,3.10−4 𝑀
0,17 1000
[C17H21O4N]= . = 5,6.10−3 M
100 303,36
Ans
Hoà tan 2 viên aspirin nên
500 1
[𝐻𝐶9 𝐻7 𝑂4 ] = . . 2 𝑣𝑖ê𝑛 = 0,0171 𝑀
325 180
Ban đầu : 0,0171 M 0M 0M
Phản ứng : −𝑥 M +𝑥M +xM
Cân bằng : 0,0171 − 𝑥 M 𝑥M 𝑥M
[𝐻3 𝑂+ ][𝐶9 𝐻7 𝑂4− ] −4
𝑥2
𝐾𝑎 = ⇔ 3,3.10 = ⇒ 𝑥 = 2,22.10−3
[𝐻𝐶9 𝐻7 𝑂4 ] 0,0171 − 𝑥
𝑝𝐻 = − log(2,22.10−3 ) = 2,65
𝐐. 𝟏𝟑 (EX 16–7A) What is the pH of 0.015 M CH2FCOOH(aq)?
CH2FCOOH + H2O = H3O+ + CH2FCOO– Ka = 2,6×10–3
Ans
Ans
114 1
[C5H11N] = . = 4,26.10−3 𝑀
315 85
𝐐. 𝟏𝟔 (EX 16-9A) Malonic acid, is a diprotic acid used in the manufacture of barbiturates
An aqueous solution that is 1.05 M has pH = 0.67. The free oxalate ion concentration in this solution is [C2O42–] =
5,3×10–5 M. Determine Ka1 and Ka2 for oxalic acid.
Ans
𝐾𝑎2 ≈ [𝐶2 𝑂42− ] = 5,3.10−5
𝐐. 𝟏𝟖 (EX 16-10)
A. Calculate [H3O+ ], [HSO4– ] and [SO42–] in 0.20 M H2SO4.
B. Calculate [H3O+ ], [HSO4– ] and [SO4 2–] in 0.020 M H2SO4. [Hint: Is the assumption that [HSO4– ] = [H3O+ ] valid?]
Ans
𝐐. 𝟏𝟗 (EX 16-11A) Predict whether each of the following 1.0 M solutions is acidic, basic, or pH neutral:
(a) CH3NH3+NO3– (aq),
(b) NaI(aq);
(c) NaNO2(aq)
Ans
(a) CH3NH3+NO3– (aq), là muối của cation base yếu nên cation CH3NH3+ sẽ bị thuỷ phân thành dung dịch có
⎯⎯
tính acid ( CH3NH3+ + H2O ⎯ ⎯→ CH3NH2 + H3O+), trong khi NO3- là base liên hợp của một acid mạnh nên
không thuỷ phân nữa. Dung dịch của chất này có tính acid.
(b) NaI tạo từ cation của base mạnh và anion của một acid mạnh nên không thuỷ phân. Nên dung dịch của
chất này có môi trường trung tính.
(c) NaNO2 được tạo bởi cation của base mạnh và anion của acid yếu nên cation bị thuỷ phân trong H2O (NO2
⎯⎯
→ HNO2 + OH-). Dung dịch của chất này có tính base.
⎯
⎯
Ans
Cocaine: 𝑝𝐾𝑎 = 14.00 - 𝑝𝐾𝑏 = 14,00 - 8,41 = 5.59, Ka = 10-5,59 = 2,6 10-6
Codeine : 𝑝𝐾𝑎 = 14.00 - 𝑝𝐾𝑏 = 14,00 - 7,96 = 6,04, Ka = 10-6,04 = 9,1 10-7
𝑝𝐻: Cadeine < Cocaine
Ans
𝐐. 𝟖 (EX 18-4B) What is the molar solubility of in a buffered solution with pH = 8.20?
Độ tan tính theo nồng độ mol của Fe(OH)3 trong dung dịch đệm có pH = 8,20
Ans
pOH = 14,00 – 8,20 =5,8→ [𝑂𝐻 − ] = 10−5,8 = 1,6 x 10-6 M
𝐹𝑒(𝑂𝐻 )3 Fe3+ + 3OH-
VÌ vậy, độ tan tính theo nồng độ mol của Fe(OH)3 trong dung dịch đệm có pH = 8,20 là 9,8 x 10-21 M.
𝐐. 𝟏𝟓 (EX 18-8B) Will a precipitate of Fe(OH)3 form from a solution that is 0.013 M Fe3+ in a buffer solution
that is 0,150 M HC2H3O2 and 0.250 M NaC2H3O2.
Hỏi kết tủa Fe(OH)3 có thể hình thành trong dung dịch chứa 0,013 M Fe3+ trong dung dịch đệm với 0,150 M
HC2H3O2 và 0,250 M NaC2H3O2?
Ans (#nguyennam94197)
Theo phương trình Henderson Hasselbalch:
[C2 H3 O−
2] 0,250 𝑀
pH = pKa + log = − log(1,8 x 10−5 ) + log ( ) = 4,96
[𝐻𝐶2 𝐻3 𝑂2 ] 0,150 𝑀
[Ag(NH3 )2 ]+ 0,15
Kf = 2 [NH3] = √ = 0,625 𝑀
[𝐴𝑔+ ][𝑁𝐻3 ] 2,4 x 10−8 x 1,6 x 107
𝐐. 𝟖 (EX20-4B) In an acidic solution, O2(g) oxidizes Cr2+(aq) to Cr3+(aq). The O2(g) is reduced to H2O(l).
°
𝐸𝑐𝑒𝑙𝑙 for the reaction is 1.653 V. What is the standard electrode potential for the couple Cr3+/Cr2+?
Ans
°
0,0592
𝐸𝑐𝑒𝑙𝑙 = . 𝑙𝑜𝑔𝐾 = +2,016 → 𝐾 = 10204,324
6
Hằng số quá lớn nên chắc chắc kim loại Al có thể đẩy hoàn toàn ion Cu2+ ra khỏi dung dịch.
𝐐. 𝟐𝟐 (EX20-11B) Calculate Ksp the given the following concentration cell information.
Tính tích số tan của PbI2 sử dụng thông tin pin nồng độ sau: PbPb2+ (PbI2 bh)║Pb2+(0.100 M)Pb(r) Epin =
0.0567 V
Ans
⎯⎯
→ Pb2+ + 2I- → 𝐾𝑠𝑝 = [𝑃𝑏2+ ][𝐼− ]2
PbI2 ⎯
⎯
Anode: 𝑃𝑏(𝑟) → 𝑃𝑏2+ + 2𝑒 −
Catode: 𝑃𝑏2+ + 2𝑒 − → 𝑃𝑏(𝑟)
Do cân bằng ở 2 đầu điện cực nên điện cực pin chuẩn bằng 0
Số e trao đổi là n = 2. Theo phương trình Nest :
0,0592 [𝑃𝑏2+ ]𝑎𝑛𝑜𝑑𝑒 0,0592 [𝑃𝑏2+ ]𝑎𝑛𝑜𝑑𝑒
𝐸𝑐𝑒𝑙𝑙 = 𝐸 0 − . log ( ) = 0 − . log ( ) = 0,0567
𝑛 [𝑃𝑏2+ ]𝑐𝑎𝑡𝑜𝑑𝑒 2 0,1
→ [𝑃𝑏2+ ]𝑎𝑛𝑜𝑑𝑒 = 0,0012𝑀 → [𝐼− ] = 0,0024𝑀 → 𝐾𝑠𝑝 = (0,0012). (0,0024)2 = 6,9.10−7
𝐐. 𝟑𝟔 (E58) Dựa vào bảng thế điện cực chuẩn, hãy tính giá trị sức điện động của các hệ pin sau
a) Zn – Br2
b) Li – F2
Ans
a)
0,002
∆𝐺 ° = −𝑛𝐹. 𝐸 ° = −𝑅𝑇𝑙𝑛𝐾 → −2.96500.0,002 = −2,303.8,314.298. 𝑙𝑜𝑔𝐾 → 𝐾 = 1,169
[𝑁𝑖 2+ ][𝑉 2+ ]2
𝐾 = 1,263 =
[𝑉 3+ ]2
b)
-0,128
−5
[𝑀𝑛2+ ]𝑃{𝐶𝑙2 (𝑔)}
𝐾 = 4,68.10 =
[𝐶𝑙 − ]2 [𝐻 + ]4
c)
Khử: Ag+ + e- ⎯⎯
→ Ag(s) 𝐸 ° = +0,800 𝑉
𝐸𝑎° = +0,361𝑉
→ 𝐸𝑏° = −0,255𝑉
Thus, 𝐸 ° = −0,255 𝑉