Академический Документы
Профессиональный Документы
Культура Документы
AB + CD
AD + BC
Reactions that can be traversed in both directions are said to reversible. Theoretically at least, all chemical reactions are reversible.
Reversible Reactions
HgO
Hg HgO HgO HgO HgO HgO Hg O2 HgO Hg O2 HgO HgO
HgO
Hg
2 HgO (s)
2 Hg (l) + O2 (g)
Reversible Reactions
2 HgO (s) 1 2 2 Hg (l) + O2 (g)
Upon heating, mercury (II) oxide decomposes to mercury (Hg) and oxygen (O2) [ Equation 1]: 2 HgO (s) 2 Hg (l) + O2 (g)
Under the same conditions, mercury (Hg) and oxygen (O2) recombine form mercury (II) oxide again [Equation 2]: 2 Hg (l) + O2 (g) 2HgO (s)
Mercury and oxygen combine to form mercury oxide just as fast as mercury oxide decomposes into mercury and oxygen
Reversible Reactions
2 HgO (s) 2 Hg (l) + O2 (g)
Reversible Reactions
H2 + I 2 2 HI 2 HI H2 + I 2 Synthesis of Hydrogen Iodide Dissociation of Hydrogen Iodide
Examine the two sets of plots carefully, noting which substances have zero initial concentrations, and are thus "reactants" in each case. Satisfy yourself that these two sets represent the same chemical reaction system, but with the reactions occurring in opposite directions. Most importantly, note how the concentrations of all the components are identical when the system reaches equilibrium.
Reversible Reactions
H2 + I2 2HI
The equilibrium state is independent of the direction from which it is approached. Whether we start with an equimolar mixture of H2 and I2 (left)
or a pure sample of hydrogen iodide (shown on the right, using twice the
initial concentration of HI to keep the number of atoms the same), the composition after equilibrium is attained (shaded regions on the right) will be the same.
For more information, Click Here
The stronger the bond between the elements of a certain molecule, the harder it is to break in a chemical reaction, and the slower the reaction.
A mixture of iron and sulfur doesnt react unless strongly heated. An elevation in the temperature makes the reaction goes faster by increasing the frequency of collisions between reacting particles. In general all reactions, especially endothermic (because they absorb energy) ones occur much more quickly when heated. This is due to the fact that heat gives enough energy to break or form bonds between different atoms.
A catalyst speeds the rate of any reaction without affecting its products.
Hydrogen peroxide is an antiseptic that decomposes spontaneously into water and oxygen: 2H2O2 (l) 2H2O (l) + O2 (g) Because the reaction is slow, H2O2 can be conserved for many months. But when a platinum wire is immersed in H2O2 solution, oxygen gas release is observed on the platinum surface.
Interpretation: Who can give an interpretation??? As the surface area decreases, the reacting molecules become closer increases the frequency of collision between molecules New molecules are formed
b) Increasing the concentration of a product shifts an equilibrium to the reactant (or left hand) side because the rate of the reverse reaction is speeded up. c) Decreasing the concentration of a reactant (by removal or by compounding it with something else or by precipitation) shifts an equilibrium to the reactants (or left hand) side because the forwards reaction is slowed down. The reverse reaction will 'overtake' the forwards reaction. d) Decreasing the concentration of a product shifts an equilibrium to the products (or right hand) side because the reverse reaction is slowed and the forwards reaction 'overtakes'.
Initially (t = 0), [A] and [B] were maximum, while [C] and [D] were zero. The rate of the forward reaction decreases as A and B are used up. The rate of the reverse reaction increases as C and D are formed. Equilibrium is attained when the two rates become equal [C], and [D] remain constant at equilibrium. [A], [B],
[C] x [D]
K = ------------[A] x [B]
If the value of K is very small, the forward reaction occurs only very slightly before equilibrium is established, and the reactants are favored. A very large value of K indicates an equilibrium in which the original reactants are largely converted to products.
The numerical value of K for a particular equilibrium system is obtained experimentally.
Given [N2]=0.1M,[H2]=0.125M, [NH3]=0.11M The equilibrium constant is given by the expression: [NH3]2 K = ------------------
[N2] [H2]3
K = [O2]
[HI]2 [13.544 x 10-3]-2 K = ------------ = ---------------------------------------- = 54.47 [H2] [I2] [4.5647 x 10-3] [0.7378 x 10-3]
K < K equilibrium
** K = 0.3 < 1 this means that the reactants NO2 and SO2 are favored. In
on equilibrium systems.
Le Chataliers principle states: If a system at equilibrium is subjected to a stress, the equilibrium is shifted in the direction that relieves the stress. If you are stressed, what do you do?
Of course, you will go to a place where you can relax and relieve
the stress. The same concept is applied on the equilibrium of a chemical reaction?
1. Effect of temperature
Changes in the temperature of the system affect the position of the equilibrium by changing the magnitude of the equilibrium constant for the reaction. Increasing the temperature of a reaction that gives off heat is the same as adding more of one of the products of the reaction. It places a stress on the reaction, which must be alleviated by converting some of the products back to reactants. If the temperature of the system in equilibrium is lowered, the reaction will move in a direction to produce more heat, i.e. the exothermic reaction is favored.
of particles present.
A reaction at equilibrium was subjected to a stress results in an increase in the total pressure on the system. The reaction then shifted in the direction that minimized the effect of this stress. The reaction shifted toward the products because this reduces the number of particles in the gas, thereby decreasing the total pressure on the system.
Both the forward and backward reactions are speeded up in the same amount; therefore, there is no effect on the position of
How is equilibrium restored in following system in each of the following cases? a) A decrease in the concentration of N2 b) An increase in temperature c) An increase in the total pressure of the system
If 0.06 moles of IBr are placed in a 0.5 liter container, and the equilibrium constant K is 8.5x10-3, find the concentrations of IBr, I2, and Br2 at equilibrium.
# of moles of Br2 = 0
At equilibrium (tequi): # of moles of IBr = 0.06 2n # of moles of I2 = n # of moles of Br2 = n 2 IBr (g) I2 (g) + Br2 (g)
At t = 0:
At teq. :
0.06 moles
(0.06 2n) mole
0 mole
n mole
0 mole
n mole
Note: The coefficient of n is always the same as the coefficient of the substance.
[I2] [Br2] K = ---------------[IBr] # of moles of I2 n [I2] =----------------------- = ----------Volume 0.5 # of moles of Br2 n [Br - 2] = ----------------------- = ---------Volume 0.5 # of moles of IBr (0.06 -2n) [IBr] = ----------------------- = ------------Volume 0.5
[I2] = [Br2] = n / 0.5 = (4.67 x 10-3 ) / 0.5 = 9.34 x 10-3 M [IBr] = (0.06 2n)/0.5 = [0.06 2(4.67 x 10-3)] / 0.5 = 0.101 M
1.
2.
HCO3- + H3O+
AgCl (s) +
NaNO3
The ionic equation Na+ + OH- + H3O+ + ClThe net ionic equation H3O+ + OH2 H2O (l)
CH3COO- + H3O+
When sodium acetate is dissolved in the acetic acid solution, the concentration of the acetate ion (CH3COO-) on the right side of the equation will increase. The equilibrium will shift to the right (backward) so as to decrease the concentration of the added ion More CH3COOH is formed the concentration of H3O+ in solution decreases pH increases.
The portion of HA that dissociates into the ions depends on the acid ionization percentage and on its concentration: x=c HA + H2O t=0 t eq c c c H3 O+ + A 0 c 0 c
[A-][H3O+] Ka = ---------------[HA]
The weaker the acid is, the smaller the value of Ka and , due to the fewer number of ionized species in the numerator.
Ka = c2 / 1
Ka = c 2
[H3O+]2 Ka = ---------------c
[H3O+]2 = Ka . c
[H3O+] = Ka . c
[A-][H3O+] Ka = ---------------[HA]
Ka = c 2 [H3O+] = Ka . c
The portion of B that dissociates into the ions depends on the base ionization percentage and on its concentration: x=c B + H 2O t=0 t eq c c c BH+ + OH0 c 0 c
[OH-][BH+] Kb = ---------------[B]
The weaker the base is, the smaller the value of Kb and , due to the fewer number of ionized species in the numerator.
Kb = c 2
[H3O+] = Kb . c
Ka. Kb = Kw
Consider any weak acid, HA, in water: HA + H2O H3O+ + A-
[A-][H3O+] Ka = ---------------[HA]
Ka x Kb = [H3O+] [OH-] = Kw
This formula is always true, and can be directly applied.
a) Kb = c . 2
[OH-] = 0.048 M
Buffers
Buffers are special type of solutions made up of a weak acid and the salt of its conjugate base, or of a weak base, mixed with the salt of its conjugate acid. Examples of Buffers may include: 1. Acetic acid (HC2H3O2) mixed with sodium acetate (NaC2H3O2)
Weak acid Conjugate base
Buffers
Buffers resist changes in pH when an acid or a base is added in small amounts. Suppose a diluted acid is added in small amounts to a buffer made of HC2H3O2 and NaC2H3O2. HC2H3O2 + H2O H3O+ + C2H3O2-
When the diluted acid is added to the buffer, the concentration of [H3O+] on the left side of the equation increases reducing the concentration of H3O+ ions According to Le Chatelier principle, the equilibrium will shift to the right, thus The pH will remain at
Buffers
HC2H3O2 + H2O H3O+ + C2H3O2-
Now, when a base is added to the solution, it will react with H3O+ ions causing a decrease in their concentration According to Le Chatelier
principle, the equilibrium will shift to the right to increase the concentration of H3O+ ions pH will return to its original value.
Solubility equilibrium
Solubility is defined as the amount of salt (in grams) that can be dissolved in 100 g of water. In general, salts are classified into 3 broad categories: 1. Soluble, when more than 1g of the salt can dissolve in a 100 g of water. 2. Insoluble, when less than 0.1g of the salt can dissolve in a 100 g of water. 3. Slightly soluble when the mass of salt dissolved in a 100 g of water falls between 0.1g and 1g.
Solubility equilibrium
A saturated solution is defined as a solution that contains the maximum amount of salt dissolved in water. Saturated solutions exhibit the behavior of equilibrium system, since some of the salt is dissolved in water, while the rest is precipitated in the bottom of the beaker.
Solubility equilibrium
Consider the case of silver chloride (AgCl) having a solubility of 8.9 x 10-1 g/100 g of water AgCl is considered insoluble in water AgCl (s) Ag+ + ClK [AgCl] = [Ag+] [Cl-]
K and [AgCl] are considered to be constant (since AgCl is a solid, so its concentration does not affect the equilibrium):
Solubility equilibrium
Ksp = [Ag+] [Cl-]
The solubility-product constant is then the product of the molarities of the ions in a saturated solution, each ion being raised to the power of its coefficient. Exercise 9 : Find the expression of the Ksp of calcium fluoride, CaF2 CaF2 Ca2+ + 2F-
Solubility equilibrium
The lower the Ksp, the less soluble the salt is. Least soluble
Most soluble
Solubility equilibrium
AgCl (s) t=0 teq M Mc Ag+ + Cl0 c 0 c M = initial concentration
Ksp = [Ag+] [Cl-] = c . c = c2 c is the molarity in mole/l , while the solubility is in given in
Solubility equilibrium
Exercise 10: Find the Ksp of CaF2 if its solubility is 1.7 x 10-3g/100 g of water.
Ca = 40
F = 19
Ca2+ + 2F0 c 0 2c
Solubility equilibrium
1.7 x 10-3 c = --------------78 x 0.1 c = [Ca2+] = 2.18 x 10-4 mole/l
Solubility equilibrium
Exercise 11: Find the solubility of cadmium sulfide, CdS, in g/100g
Ksp = [Cd2+][S2-] = c . c = c2
c = Ksp = 8 x 10-27
c = 8.944 x 10-14 M
Solubility equilibrium
Molecular weight of CdS = 112 + 32 = 144 g / mole mass of CdS c = ---------------------------------------------(Molecular weight of CdS) x 0.1L mass of CdS 8.944 x 10-14 = ------------------144 x 0.1
Solubility equilibrium
Exercise 12: Find the solubility of CdS in mole/l, given its Ksp to be 8 x 10-27 CdS Cd2+ + S2-
t=0 teq
M Mc
0 c
0 c
Ksp = [Cd2+][S2-] = c . c = c2
c = Ksp = 8 x 10-27
c = 8.944 x 10-14 M
Solubility equilibrium
Precipitation calculation
A precipitate is the formation of an insoluble salt in solution. The precipitate may form when mixing two soluble salts.
XY
X+ + Y-
Solubility equilibrium
Exercise 13: Will a precipitate form when 20 ml of 0.01M BaCl2 is mixed with 20 ml of 0.005M Na2SO4? Ksp of BaSO4 = 1.1 x 10-10?
The dissolution reaction of the precipitate formed is: BaSO4 (s) Ba2+ + SO42-
Solubility equilibrium
# moles of BaCl2 [BaCl2] = ----------------------volume of BaCl2 # moles of BaCl2 0.01 = ------------------------20 x 10-3 L
# moles of BaCl2 = 2 x 10-4 moles # moles of BaCl2 = # moles of Ba2+ = 2 x 10-4 moles [Ba2+] = (# moles of Ba2+) / (total volume) = (2 x 10-4) / (40 x 10-3 L) [Ba2+] = 5 x 10-3 M
Solubility equilibrium
# moles of Na2SO4 [Na2SO4] = ------------------------volume of Na2SO4 # moles of Na2SO4 0.005 = ------------------------20 x 10-3 L
# moles of Na2SO4 = # moles of SO42- = 1 x 10-4 moles [SO42-] = (# moles of SO42-) / (total volume) = (1 x 10-4) / (40 x 10-3 L) [SO42-] = 2.5 x 10-3 M
Solubility equilibrium
[Ba2+] [SO42-] = (5 x 10-3) (2.5 x 10-3) = 1.25 x 10-5 [Ba2+] [SO42-] = 1.25 x 10-5 Ksp = 1.1 x 10-10