KESETIMBANGAN KIMIA REVIEW (4 TO 6)

JURUSAN TL-ITS

Kesetimbangan

Persamaan reaksi hanya menyatakan hubungan jumlah (kuantitas) dari zatzat yang bereaksi dengan zatzat hasil reaksi secara stoikiometri. Kinetika serta termodinamika reaksi mempelajari berapa lama suatu reaksi akan berlangsung dan ke arah mana yang paling mungkin terjadi Kesetimbangan ini akan terjadi jika jumlah Pembentukan sama dengan jumlah yang teruraiEQUILIBRIUM.

Cont
A

dynamic equilibrium consists of a forward reaction, in which substances react to give products, and a reverse reaction, in which products react to give the original reactants. equilibrium is the state reached by a reaction mixture when the rates of the forward and reverse reactions have become equal.

Chemical

A Problem to Consider

Applying Stoichiometry to an Equilibrium Mixture. we place 1.000 mol N2 and 3.000 mol H2 Suppose
in a reaction vessel at 450 oC and 10.0 atmospheres of pressure. The reaction is

N 2 ( g ) 3H 2 ( g )

2NH 3 (g)

What is the composition of the equilibrium mixture if it contains 0.080 mol NH3?

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A Problem to Consider

Using the information given, set up the following table.

N 2 ( g ) 3H 2 ( g )

2NH 3 (g)

Starting 1.000 3.000 Change -x -3x Equilibrium 1.000 - x 3.000 - 3x

0 +2x 2x = 0.080 mol

The equilibrium amount of NH3 was given as 0.080 mol. Therefore, 2x = 0.080 mol NH3 (x = 0.040 mol).
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A Problem to Consider

Using the information given, set up the following table.

N 2 ( g ) 3H 2 ( g )
Starting 1.000 3.000 Change -x -3x Equilibrium 1.000 - x 3.000 - 3x

2NH3 (g)
0 +2x 2x = 0.080 mol

Equilibrium amount of N2 = 1.000 - 0.040 = 0.960 mol N2 Equilibrium amount of H2 = 3.000 - (3 x 0.040) = 2.880 mol H2 Equilibrium amount of NH3 = 2x = 0.080 mol NH3
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The Equilibrium Constant

Every reversible system has its own position of equilibrium under any given set of conditions. The ratio of products produced to unreacted reactants for any given reversible reaction remains constant under constant conditions of pressure and temperature. The numerical value of this ratio is called the equilibrium constant for the given reaction.
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The Equilibrium Constant

The equilibrium-constant expression for a reaction is obtained by multiplying the concentrations of products, dividing by the concentrations of reactants, and raising each concentration to a power equal to its coefficient in the balanced chemical equation.

aA bB

cC dD
[C] [D] Kc a b [ A ] [B ]
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For the general equation above, the equilibrium-constant expression would be:

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The Equilibrium Constant

The equilibrium-constant expression for a reaction is obtained by multiplying the concentrations of products, dividing by the concentrations of reactants, and raising each concentration to a power equal to its coefficient in the balanced chemical equation.

aA bB

cC dD
[C] [D] Kc a b [ A ] [B ]
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The molar concentration of a substance is denoted by writing its formula in square brackets.
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The Equilibrium Constant

The equilibrium constant, Kc, is the value obtained for the equilibrium-constant expression when equilibrium concentrations are substituted.
A large Kc indicates large concentrations of products at equilibrium. A small Kc indicates large concentrations of unreacted reactants at equilibrium.

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Obtaining Equilibrium Constants for Reactions

Equilibrium concentrations for a reaction must be obtained experimentally and then substituted into the equilibrium-constant expression in order to calculate Kc.

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Obtaining Equilibrium Constants for Reactions

Consider the reaction below

CO(g ) 3 H 2 (g)

CH 4 (g) H 2O(g)

Suppose we started with initial concentrations of CO and H2 of 0.100 M and 0.300 M, respectively.
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Obtaining Equilibrium Constants for Reactions

Consider the reaction below

CO(g ) 3 H 2 (g)
Reactants [CO] = 0.0613 M [H2] = 0.1893 M

CH4 (g) H 2O(g)

Products [CH4] = 0.0387 M [H2O] = 0.0387 M
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When the system finally settled into equilibrium we determined the equilibrium concentrations to be as follows.

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Obtaining Equilibrium Constants for Reactions

Consider the reaction below (see Figure 15.5).

CO(g ) 3 H 2 (g)

CH4 (g) H 2O(g)

The equilibrium-constant expression for this reaction is:

[CH 4 ][H 2O] Kc 3 [CO][H 2 ]

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Obtaining Equilibrium Constants for Reactions

Consider the reaction below (see Figure 15.5).

CO(g ) 3 H 2 (g)

CH4 (g) H 2O(g)

If we substitute the equilibrium concentrations, we obtain:

(0.0387M )(0.0387M ) Kc 3.93 3 (0.0613M )(0.1839M )

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The Equilibrium Constant, Kp

In discussing gas-phase equilibria, it is often more convenient to express concentrations in terms of partial pressures rather than molarities
It can be seen from the ideal gas equation that the partial pressure of a gas is proportional to its molarity.

n P ( )RT MRT V

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The Equilibrium Constant, Kp

If we express a gas-phase equilibria in terms of partial pressures, we obtain Kp.

Consider the reaction below.

CO(g ) 3 H 2 (g)
Kp PCH
4

CH4 (g) H 2O(g) PH O

2

PCO PH

3
2

The equilibrium-constant expression in terms of partial pressures becomes:

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The Equilibrium Constant, Kp

In general, the numerical value of Kp differs from that of Kc.

From the relationship n/V=P/RT, we can show that
Dn

K p K c ( RT)

where Dn is the sum of the moles of gaseous products in a reaction minus the sum of the moles of gaseous reactants.

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A Problem to Consider

Consider the reaction

2SO 2 (g ) O 2 (g )
We know that

2 SO 3 (g)
Dn

K p K c ( RT)

From the equation we see that Dn = -1. We can simply substitute the given reaction temperature and the value of R (0.08206 L.atm/mol.K) to obtain Kp.
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A Problem to Consider

Consider the reaction

2SO 2 (g ) O 2 (g )
Since

2 SO 3 (g)
Dn
-1

K p K c ( RT)
K p 2.8 10
2 Latm (0.08206 molK

1000 K) 3.4
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Equilibrium Constant for the Sum of Reactions

Similar to the method of combining reactions that we saw using Hesss law, we can combine equilibrium reactions whose Kc values are known to obtain Kc for the overall reaction.
With Hesss law, when we reversed reactions or multiplied them prior to adding them together, we had to manipulate the DHs values to reflect what we had done. The rules are a bit different for manipulating Kc.
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Equilibrium Constant for the Sum of Reactions

1.

If you reverse a reaction, invert the value of Kc. If you multiply each of the coefficients in an equation by the same factor (2, 3, ), raise Kc to the same power (2, 3, ). If you divide each coefficient in an equation by the same factor (2, 3, ), take the corresponding root of Kc (i.e., square root, cube root, ). When you finally combine (that is, add) the individual equations together, take the product of the equilibrium constants to obtain the overall Kc.
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2.

3.

4.

Equilibrium Constant for the Sum of Reactions

For example, nitrogen and oxygen can combine to form either NO(g) or N2O (g) according to the following equilibria.

(1) (2)

N 2 (g ) O 2 (g )

2 NO(g)

Kc = 4.1 x 10-31 Kc = 2.4 x 10-18

N 2 (g ) 1 O 2 (g ) 2

N 2O(g)

Using these two equations, we can obtain Kc for the formation of NO(g) from N2O(g):

(3)

N 2 O( g ) 1 O 2 ( g ) 2

2 NO(g)

Kc = ?
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Equilibrium Constant for the Sum of Reactions

To combine equations (1) and (2) to obtain equation (3), we must first reverse equation (2). When we do we must also take the reciprocal of its Kc value.

(1) (2) (3)

N 2 (g ) O 2 (g )

2 NO(g)
1 O (g ) 2 2

Kc = 4.1 x 10-31
Kc =
1 2.4 10-18

N 2O(g)

N 2 (g)

2 NO(g) 1 31 K c (overall ) (4.1 10 ) ( ) 1Houghton Mifflin .7 1013 18 2.41524 Copyright rights reserved. 10 Company.All Presentation of Lecture Outlines,

N 2O(g ) 1 O 2 (g ) 2

Heterogeneous Equilibria

A heterogeneous equilibrium is an equilibrium that involves reactants and products in more than one phase.
The equilibrium of a heterogeneous system is unaffected by the amounts of pure solids or liquids present, as long as some of each is present. The concentrations of pure solids and liquids are always considered to be 1 and therefore, do not appear in the equilibrium expression.
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Kc - ignoring solids and liquids

Kc calculations involve: 1) Concentrations in mol/L, 2) Gaseous products and reactants For gases, if mol or L changes so does mol/L Q - If a gas is 1 mol/L, what is its new [ ] if its compressed to 1/2 of its original volume? A - Now we have 2 mol/L (e.g. 1 mol / 0.5 L) Conversely, solids and liquids dont compress Q - If a solid is initially 1 mol/L, what is the concentration if the volume is reduce to 1/2? A - To get half the volume we must cut it in half we still have 1 mol/L (e.g. 0.5 mol / 0.5 L) Concentrations of liquids and solids do not change. Concentrations of ions and gases do.

Heterogeneous Equilibria

Consider the reaction below.

The equilibrium-constant expression contains terms for only those species in the homogeneous gas phaseH2O, CO, and H2.

C(s ) H 2O(g )

CO(g) H 2 (g)

[CO][H 2 ] Kc [ H 2O ]
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Precipitation

Pelarutan atau kelarutan endapan Endapan adalah zat atau materi yang memisahkan diri sebagai fase padat dari sistem larutan. Fase padat ini dapat terjadi dalam bentuk kristal, bentuk tersuspensi, maupun bentuk koloid. Centrifuge, Filtrasi, Flotation and Sedimentation.

Faktor yang mempengaruhi...

Solubility Zat padat yang ditambahkan tidak mampu lagi larut dalam pelarutnya - Ksp Ion sekutu ionion dari zat lain yang merupakan bahan endapan

Ksp

Larutan yang sudah tidak mampu lagi melaruitkan zat terlarut ini dinamakan larutan jenuh, yaitu larutan yang ionionnya telah mencapai kesetimbangan antara melarut dan mengkristal IAP RT IAP SI log DG ln Ksp n Ksp

2.303RT DG SI n

Cont

When SI = 0, hence DG =0, the solution is in equilibrium. When SI < 0, DG > 0, the solution is undersaturated and precipitation is impossible in solution When SI > 0, DG < 0, the solution is supersaturated and precipitation is spontaneous.

Ksp (solubility product) - background

Bottom line: 1) Ksp is similar to Kc, 2) It deals with ions instead of gases, 3) one side of the chem. equation has a solid, which is ignored We have used Kc in equilibrium problems K indicates an equilibrium c indicates units are mol/L (in this course it will also indicate we are dealing with gases) There are other types of K: Ksp, Kw, Ka, Kb Each subscript immediately indicates some detail about the equilibrium Kw: equilibrium of water, Ka: acid, Kb: base Ksp: equilibrium between solid and ions

Ksp - background
The equilibrium between solids and ions is different from the equilibrium between gases The equilibrium between solids and ions is a phase equilibrium (e.g. NaCl(aq))

Na+(aq) + Cl-(aq)

NaCl(s)

Ksp deals with a phase equilibrium: (s) (aq)

Why use Ksp instead of Kc?

Read 14.9 (574 - 575), Try PE 13 Consider: NaCl Na+(aq) + Cl-(aq)

[NaCl(s)] doesnt [Na+(aq)] [Cl-(aq)] K= change (its a konstant) [NaCl(s)]

K [NaCl(s)] = [Na+(aq)] [Cl-(aq)] Ksp = [Na+(aq)] [Cl-(aq)]

We use Ksp because it Na+(aq) + Cl-(aq) indicates that the equilibrium is a phase equilibrium (between a NaCl(s) solid and its ions)

Example
The solubility of silver sulfate is 0.014 mol/L (Ag2SO4). Calculate the Ksp. We just saw that the solubility of nickel (II) carbonate is 3.7 x 10-4 mol/L. What mass of NiCO3 is needed to prepare 500 mL of saturated solution? Mr=118.72 0.50 L of 1.0 x 105 M Pb(OAc)2 is combined with 0.50 L of 1.0 x 103 M K2CrO4. a. Will a ppt occur? Ksp(PbCrO4) = 1.8 x 101 b. Find the Eq. conc. of Pb2+ remaining in solution

Calculating the Ksp of silver sulfate

The solubility of silver sulfate is 0.014 mol/L. This means that 0.0144 mol of Ag2SO4 will dissolve to make 1.0 L of saturated solution. Calculate the value of the equilibrium constant, Ksp for this salt.

Ag2SO4 (s) 2 Ag+ (aq) + SO42- (aq)

--+ 2s 2s --+s s

Ksp = [Ag+]2[SO42-] = (2s)2(s) = (4s2)(s) = 4s3

We know: s = 0.0144 mol/L Ksp = 4(0.0144)3 = 1.2 x 10-5

Other ways to express solubility...

We just saw that the solubility of nickel (II) carbonate is 3.7 x 10-4 mol/L. What mass of NiCO3 is needed to prepare 500 mL of saturated solution?

3.7 x 10 4 mol NiCO3 0.500 L 118.72 g x x 0.022 g 1L 1mol NiCO3

0.022 g of NiCO3 will dissolve to make 500 mL solution.

Try Problems 9 - 26

Problem: 0.50 L of 1.0 x 105 M Pb(OAc)2 is combined with 0.50 L of 1.0 x 103 M K2CrO4. a. Will a ppt occur? Ksp(PbCrO4) = 1.8 x 1014 Pb(OAc)2(aq) + K2CrO4(aq) PbCrO4(s) + 2KOAc(aq) then: [Pb2+]: PbCrO4(s) Pb2+ + CrO42
-5 0.50 L 1.0 x 10 mol Pb(OAc)

Ksp= [Pb2+][CrO42]

1 Pb 2 1 Pb(OAc)2

mol Pb 2 5.0 x 106 L 1L

2 mol CrO 4L

2 [CrO42-]: 0.50 L 1.0 x 10-3 mol K 2CrO 4 1 CrO41 K 2CrO4 L

1L

5.0 x

10-4

Q = [5.0 x 10-6][5.0 x 10-4] = 2.5 x 10-9

compare to Ksp:
39

Q > Ksp

so a ppt. will occur

b. find the Eq. conc. of Pb2+ remaining in solution after the PbCrO4 precipitates. K (PbCrO ) = 1.8 x 1014
sp 4

Since [Pb2+] = 5.0 x 10-6 and [CrO42-] = 5.0 x 10-4 and there is a 1:1 stoichiometry, Pb2+ is the limiting reactant. PbCrO4(s) I. (after ppt.) C. E. Pb2+ + CrO42

0
+x

5.0 x 10-4 - 5.0 x 10-6 = 5.0 x 10-4

+x

5.0 x 104 + x
Try dropping the + x term.

Ksp = [x][5.0 x 104 + x] 1.8 x 1014 = x(5.0 x 10-4) x = [Pb2+] = 3.6 x 1011

This is the concentration of Pb2+ remaining in solution.

40

Selective Precipitation Pengendapan Sulfida Pengendapan dan Kelarutan Hidroksida

Pengedapan Sulfida
Merupakan pelarut logam Mempunyai kelarutan yang rendah di air pH mempengaruhi proses : H2S merupakan asam lemah, yang akan terdisosiasi menjadi ion H+ dan S2-, dengan konsentrasi yang bervariasi sesuai dengan keadaan pH larutan. Tahap dissosiasinya adalah :