III.

CHEMICAL EQUILIBRIUM
VARIABLES (a) Temperature (T) — Commonly used scale is Celsius (oC)[ (but Kelvin (K) scale in thermodynamics]

(b) Pressure (P) Three units of pressure are in common use: bar, atmosphere (atm) and pascal. (Pa) 1 bar = 0.987 atm = 105 Pa = 0.1 MPa The difference between the bar and the atmosphere is so small that for most purposes in geochemistry the two may considered approximately equivalent. (c) the concentration of chemical species (Xi) in the system under consideration Concentrations of solids: - Usually expressed as ppm = g/tonne Concentrations of solutes in an aqueous solution are expressed in various ways: molalilty (m) = moles of solute/ kg of solvent [for pure water, 1 liter = 1 kg] molarity (M) = moles of solute/ liter of solution parts per million (ppm) = grams/106 g = tons/106 tons = mg/106 mg (=1 kg) We will use molalilty for consistency (although in dilute solutions the difference between molalilty and molarity is insignificant in most geologic calculations).

BASIC QUESTIONS TO BE ANSWERED (a) In which direction should a chemical reaction go and why? (b) When should it stop and why? (c) Which mineral assemblage is stable and which is not at a given P-T condition, etc. (d) What happens when we disturb the equilibrium? Such questions may be answered by a variety of interrelated techniques: the Law of Mass Action (and the Equilibrium Constant); Free Energy change for reactions; Chemical potentials, etc. -- and all of them would converge on the same answer. We focus here on the simplest, and possibly somewhat familiar, technique involving equilibrium constants.

THE LAW OF MASS ACTION The Concept of Chemical Equilibrium Many chemical reactions are incomplete because they are reversible - i.e., the same final product is obtained when such a reaction is started from either end. For example, for a reversible reaction represented as A+B ⇔ Y+Z the end product would contain the same mixture of four substances whether we mix A and B or Y and Z. In modern language we would say that a reversible reaction stops when it has reached a state of chemical equilibrium. Actually, the reaction does not stop, but a dynamic equilibrium has been reached. No further change in the assemblage is observed because of a balance between the two opposing processes going at equal rates. In fact, for a chemical reaction, the terms reversibility and equilibrium are used interchangeably. An irreversible process is unidirectional. No equilibrium can be achieved in the case of an irreversible process.

22

.1a) Note that the quantities [Y]. component i in phase α) Solute (i) in a liquid solution Activity (ai) = 1 Activity (aiα). ai = mI) Ideal gas Partial pressure (Pi) = XiP [P = total pressure Xi = mole fraction of i] Fugacity (fi) = γiPi [ γιi= fugacity coefficient of i] Non-ideal gas lim fi/Pi = γi ⇒ 1 as P⇒ 0 (i. ppm. In very dilute solutions.e. the activity is almost the same as the molality.g.in the expression for Keq represent concentrations (e.e. Whether such a reaction is feasible or not has to be answered from other considerations...1b) (3. This obscure formulation has come down to us as the Law of Mass Action. The scientists who recognized this in the 1860’s. 1 component i) Solid solution (e.... the reaction can be made to go in a forward direction by adding more of A and/or B.. etc). g/liter.. Keq as defined above is only an approximate constant. which is defined as [Y]y [Z]z Keq = ---------------[A]a [B]b (3. to concentration and partial pressure.. not masses (e..). 23 . etc. the concentration of a solute in a solution is numerically very close to its activity and the partial pressure of a gas is very close to its fugacity. as we are concerned with in this chapter.g. and in the reverse direction by adding more of Y and/or Z. liters.. grams.. for very dilute solutions. and for an ideal solution.. such as Free Energy change for the reaction. all gases behave ideally at sufficiently low pressures) _____________________________________________________________________________________________ However. Actually.e. it suggested that the "driving force" of a reaction depended on the "masses" of the substances involved. respectively. These are “effective” or “thermodynamic” parameters related. ____________________________________________________________________________________________ Concentrations used for Equilibrium Constant Pure solid phases (i. depends on the solid solution Activity (ai ) = λi mI [ m = molality of i λi = activity coefficient of i] lim ai/mI = λi ⇒ 1 as mI⇒ 0 (i.g. Equilibrium Constant For a generalized reversible chemical reaction represented by the equation aA + bB ⇔ yY + zZ the state of equilibrium is represented by a quantity called the Equilibrium Constant (Keq).From a state of equilibrium. number of moles/g. to obtain the correct value of Keq. we will stick with the more familiar expressions of concentrations. we must use activities (for solid and liquid phases) and fugacities (for gaseous phases). for the present.

Feldspar weathers to kaolinite on the earth’s surface.e..2) produces CO2 that may escape into the atmosphere -. (b) Keq for a reaction is a constant at a particular P-T condition. Anhydrite dissolves in water at 250C (to a very limited extent). what would precipitate is gypsum. In fact. Generally.+ Ca2+ + H2O + CO2 (3. reactions are more sensitive to temperature than pressure (unless a fluid phase is involved in the reaction). the rate of most chemical reactions double every 10oC rise in temperature. not anhydrite.g. but from a solution saturated with anhydrite.) (d) Commonly used notation: = Balanced reaction ⇔ Reaction at equilibrium ⇒ Unidirectional reaction How will you establish that a given reaction has achieved equilibrium? 24 . we will see later that the variation of K with T and P forms the basis of geothermometry and geobarometry.There are a few more points about Keq that need to be emphasized: (a) Note that a chemical reaction is always written in terms of the number of moles of reactants and products and is balanced. As a crude general guideline.g. respectively. a reaction such as CaCO3 + 2HCl = 2Cl. (ii) the reactants and productions don't stay together long enough to achieve equilibrium (e. unidirectional reactions) because: (i) some part of the reaction process is very slow (a kinetic barrier) e... (c) Some reactions in nature may fail to reach equilibrium (i.such a reaction may run to completion. but not the other way.

then. an Equilibrium Constant has no meaning except in reference to a specific reaction.2 bars. 2.4 HCl (10-x) (1-x) There should be no problem in solving this quadratic equation for x.4 = 100. write the above reaction in several ways: 2HCl (g) ⇔ H2 (g) + Cl2 (g) K'HCl = 1/K 1/2 H2 (g) + 1/2 Cl2 (g) ⇔ HCl (g) K''HCl = (K)1/2 Thus. Now let us disturb the equilibrium by adding some H2 to the mixture so as to raise the partial pressure of H2 momentarily to 10 bars.4 || 108.5 x 108 antilog 8.5 x 108 and 108.6x108 = 108.4 x 108 = 2. Since every mole of H2 would react with another mole of Cl2 to produce 2 moles of HCl.= 2.6x10 ) = log 2. of course.4 = 108.4 at 1.6 + log 10 = 0. KHCl = PHCl2 and PHCl = √ (108.3) [HCl]2 KHCl = ----------------.2 + 2x)2 ----------------=K = 108.000oC (measured) (3. the roots are given by: -b + (b2 . PCl2 must also be reduced by x whereas PHCl will be increased by 2x.4 || 8 8 log (2. for example.4 bars) = 104.4) [H2] [Cl2] --------------------------------------------------------------------------------------------------------------------------------------------|| Equivalence of. their concentrations can be expressed as partial pressures (Pi).4 --------------------------------------------------------------------------------------------------------------------------------------------We can. So. What will be the new values of the partial pressures when equilibrium is re-established? Suppose the amount of H2 that reacts is such that the PH2 is reduced by the amount x.4 + 8 = 8.4ac)1/2 x = ----------------------------2a ____________________________________________________________________________________________ 25 . we can write (104. so that we can write KHCl = PHCl2/ PH2 PCl2 Dalton's Law of Partial Pressure: Pi = Xi P where Xi = mole fraction of i = ni / Σni ______________________________________________________________________________________________ Suppose PH2 = PCl2 = 1 bar. Always balance the reaction. Some H2 must now react with an equivalent amount of Cl2 to produce HCl (forward reaction) so that the value of KHCl is restored.EXAMPLES OF CHEMICAL EQUILIBRIUM (a) H2 (g) + Cl2 (g) ⇔ 2HCl (g) [Homogeneous equilibria — one gaseous phase] (3. This is a standard technique for calculating new concentrations of reactant and product species when the equilibrium in a system is disturbed. --------------------------------------------------------------------------------------------------------------------------------------------Assuming the gases to be ideal. _____________________________________________________________________________________________ For a quadratic equation of the form ax2 + bx + c = 0.

But.6) To evaluate KCO2.1 bar PHCl = 104.9 = 0.] (b) CO2 (g) + H2O (liq) ⇔ H2CO3 (liq) [Heterogeneous equilibria — 2 phases] (3. but make sure to explain the justification for your simplifying assumptions.4 (10-x) (1-x) = 1 10x =11 (neglecting x2) x = 0. so that 10 (1-x) = 1 x = 0. mH2O = No. so that 2x is negligible compared to 104.016 (gram molecular wt. The error will be insignificant.2 bars (neglecting x) [You should substitute these values in our equation for KHCl and see what is the error in its value.2)2 / (10-x) (1-x) = 108. 26 . the standard convention is to represent the concentration of H2O by its mole fraction in a solution. we will use a shortcut to arrive at only a slightly less precise answer. Note that x must be less than 1. Neglecting 2x from the numerator simplifies the equation to (104. You should always look for reasonable approximations while solving problems. of moles of water per 1 kg (=1000 g) of water = 1. because it governs the distribution of CO2 between the hydrosphere and the atmosphere.1 bar PCl2 = 1 . this is not strictly correct). and to use equilibrium constants consistent with this convention. it is always a good idea to check the reasonableness your assumptions by back-substitution.2. the new values of partial pressures when the equilibrium is re-established (K = 108. to save time.91 We can even use another approximation that x is fairly small compared to 10 and therefore can be neglected. The equilibrium constant for this reaction is: [H2CO3] ------------[CO2] [H2O] mH2CO3 -----------------PCO2 mH2O KCO2 = = (3.4): PH2 = 10 .90 (accurate enough !) So.9 = 9.0.5 / 1 = 55. as we will see later on. mH2O = 1 (2) It is convenient to adopt the convention that dissolved CO2 is all H2CO3 (although. we use two standard conventions: (1) Actually. Also.5) This is a very important reaction for the geochemical cycle of carbon.0. of H2O) / 1 = 55. and in all dilute solutions this mole fraction is approximately 1 So.5 But.000/18.

But. K = 10-1. in the literature. at given P (total) and T.0003 Substituting.03/100 = 0.031 and PCO2 = 1 bar in the equation for KCO2 KCO2 = mH2CO3/1 = 0.031 mole/kg of water Since 1 mole of CO2 produces 1 mole of H2CO3. A molality of 10-5m seems to be a very small concentration of H2CO3 acid in normal surface water.5 Thus. for the reaction CO (g) + H O (liq) ⇔ H CO (liq) at 25oC and 1 bar.5 = 0. Atmosphere contains 0. qualitatively. and vice versa.5 liters 0.0003 = 10-1. This is an important conclusion.5 x 10-3. mH2CO3= 0. even when no gas phase is present.76/24. there is a corresponding equilibrium value of mH2CO3 (or aH2CO3). the higher the value of mH2CO3. the equation for KCO2 can now be written as: KCO2 = mH2CO3/PCO2 (3.0003 Assuming that mole fraction of CO2 ≈ volume fraction of CO2. We will take this up later. molality of CO2)? The volume of 1 mole of any gas at 25oC and 1 bar pressure = 24.76 liter of CO2/liter of water (= 1 kg of water) at 25oC and PCO2= 1 bar So. A relevant question: what is the pH of water in equilibrium with atmospheric CO2? The answer is complicated by the fact that the pH of the solution will be related to the dissociation of H2CO3: H2CO3 = HCO3.e. Thus. water in equilibrium with the present atmosphere should contain 10-5m of CO2/kg of water. XCO2 = 0. Note that the higher the value of PCO2 .7) This relation establishes that. mH2CO3 = 0.+ H+. should you expect the Precambrian ocean water to have been more acidic or less acidic compared to the present? 27 .031= 10-1. but it is sufficient to make natural waters much better weathering agents than pure water. for the time being. it should be much less as the atmospheric PCO2 is much less than the 1 bar assumed for the earlier calculation.76 liters of CO2 under these conditions = 0. Let us consider this reaction at T = 25oC and PCO2 = 1 bar What is the value of mH2CO3? Solubility of CO2 is: 0.0003 x 1 = 0. Assumption: mH2CO3 (the molality of H2CO3 dissolved in water) is determined solely by the equilibrium between water and atmospheric CO2.031 mole/kg of water Substituting the values of mH2CO3= 0.031 x 0.Thus. Let us calculate how much H2CO3 can be present in water exposed to ordinary atmosphere? Qualitatively. how many moles of CO2 per 1 kg of water (i. the higher the value of mH2CO3.5 2 2 2 3 eq This is an important conclusion that will be used frequently in this course.. volume fraction of CO2 in atmosphere = 0.0003 PCO2 = XCO2 x P (atmospheric pressure) = 0. for every PCO2 (or fCO2).031 So.5 = 10-5m Thus. Note that the higher the value of PCO2.03% CO2 by volume So. it is quite common to report mH2CO3 (or aH2CO3) as the corresponding PCO2 (or fCO2). KCO2 = mH2CO3/PCO2 = 0.

the water cannot dissolve any more CaSO4).g... very little amount) will dissolve in the water — a dissociation reaction represented as: CaSO4 = Ca2+ + SO42– So. it dissociates into the anions and cations of the acid and the base from which it was derived. the water is saturated with (dissolved) CaSO4 (i. ____________________________________________________________________________________________ The Concept of Solubility Let us conduct an experiment at by putting a lump of CaSO4 (anhydrite) crystals in a beaker of pure water at room temperature (25oC).in this case). we will get a graph as shown above: mCa2+ increasing with time up to a certain point and then staying at a constant value as equilibrium is established between the CaSO4 and the water.S . If we monitor the concentration of Ca2+ as a function of time. At this point. but their concentration is very low in most cases and may be ignored. The solution may also contain neutral molecules of the salt. Some amount of CaSO4 (actually. [Remember that in order to measure or calculate solubility of a species. how much CaSO4 has dissolved in the water after a given time can be determined by measuring the concentration (e. 28 . Concentration of Ca2+ in the water (mCa2+) Equilibrium Disequilibrium Time SOLUBILITY —SOLUBILITY PRODUCT Solubility = the amount of a compound (or an ionic species) that dissolves in a saturated solution. the system must be at equilibrium. because every mole of dissociated CaSO4 gives rise to 1 mole of Ca2+ and 1 mole of SO42-). molality) of Ca2+ in the water (or of SO42.e.] When a salt dissolves in water.

For example. The concentrations of Ca2+ and SO42.in the water.in the saturated solution of CaSO4 ____________________________________________________________________________________________ CaSO4(s) ⇔ Ca2+ (aq) + SO42.12) (3. Solubility of CaSO4 in pure water = K1/2 = (3. Solubility of CaSO4 = mCa2+ = mSO42-– Since mCa2+. this is not true for geologic environments because most natural waters contain Ca2+ and SO42.8 x 10-3m Note that this figure represents the solubility of CaSO4 when it is the sole source of Ca2+ and SO42.11) (3. In general.in the aqueous solution can be represented by molalities.mSO42-= Ksp (CaSO4)= 3.e. KCaSO4 = mCa2+ mSO42This kind of equilibrium constant is called a Solubility Product (Ksp) For any slightly soluble salt (so that the solution is a very dilute one). a saturated solution (how will you test the attainment of equilibrium?).The solubility of CaSO4 is the number of moles of CaSO4 that will dissolve in pure water (at a given temperature — 25oC in this experiment) to make the water (actually. we consider the concentration of the pure solid to be essentially constant (can you figure out the reason?) and assign a value of 1 to this constant concentration (this convention does not apply to impure solids or solid solutions).(aq) [heterogeneous equilibria — 2 phases] (3.4 x 10-5 = 10-4. 29 . [Ca2+] [SO42-] KCaSO4 = ------------------------[CaSO4] = 3. now an aqueous solution) saturated with respect to CaSO4 The solubility is determined by measuring the concentration of one of the dissociated species in the saturated solution.5 at 25oC and 1 bar (3. AgCl ⇔ Ag+ + ClCaF2 ⇔ Ca2+ + 2FAs2S3 ⇔ 2As3+ + 3S2Ksp (AgCl) = mAg+ mClKsp (CaF2) = mCa m F Ksp (As2S3) = m2As3+ m3S22+ 2 - (3.from other sources..10) (3.9) In a saturated solution.8) Assuming equilibrium — i.13) (a) What is the solubility of CaSO4 (a salt) in pure water at 25oC and 1 bar? Since every mole of CaSO4 on dissolution gives 1 mole each of Ca2+ and SO42-.4 x 10-5)1/2 = 5. a similar constant product of ionic concentrations at equilibrium can be set up. For this experiment. Solubility of CaSO4 = mCa2+ in the solution saturated with CaSO4 = mSO42.4 x 10-5 = (solubility)2.

some CaSO4 should precipitate out of this solution. The amount of CaSO4 that will precipitate = 6.x] [((7x10-3) . Is this solution saturated with respect to Ca2+? Ion Activity Product (IAP) = mCa2+ mSO42.x] [((7x10-3) . Let us check.5 x2 .5.5 = mCa2+.5 Since IAP > Ksp. we accept x2. which are controlled by pH): Saturation Index (S. IAP of CaSO4 in this solution should be the same as Ksp (CaSO4) = 10-4.I.(b) How much CaSO4 is dissociated % dissociation = Amt of CaSO4 dissociated / Amt of CaSO4 originally present = [(5.645) 10-2] [(7 .355 x 10-2] [0.0.] Compare IAP of CaSO4 in the given solution with Ksp (CaSO4) = 10-4. the concentrations of the ions at equilibrium will become: mCa2+ = (5x10-2) .x] = 10-4.05 x 10-2 x2 = 6.= (7x10-3) – x Since.x mSO42. (d) How much CaSO4 would precipitate from the solution for restoration of the equilibrium between CaSO4 and solution? [Actually. we will precipitate gypsum (CaSO4.. there should be equilibrium established between CaSO4 and water -i. That is. but we will ignore this fact as it does not make any difference in our calculations.55 x 10-3] = 2.6 30 . = 1 S.45 x 10-3)] = [(5 .45) 10-3] = [4.(6.5 = 0 x2 . Ksp (CaSO4) = 10-4.45 [We are. at equilibrium. [(5x10-2) .I. the water sample is supersaturated with CaSO4.5 x10-2 x . The new IAP = [(5x10-2) .) = Ion Activity Product / Solubility Product Supersaturated: Saturated: Undersaturated: S.39 x 10-5 = 10-4.8 x 10-3 / 1) x 100] = 0.I.(7 x 10-3 .18 x10-4) = 0 The two roots of this quadratic equation are: x1 = 5.45 x 10-3 x1 will make the values of mCa2+.] Let x = moles of CaSO4 that will precipitate Then.45 x 10-3 moles/kg water [After this amount of CaSO4 has precipitated.e. using concentrations.45 x 10 -3)] .I.6. at room temperature.mSO42-. > 1 S.2H2O) rather than anhydrite.7 x10-3 x + 35 x10-5 .= (5x10-2m) (7x10-3) = 35x10-5 = 10-3. So.(5.(6. of course.7 x 10-2)x + (3.and mSO42.10-4. < 1 IAP > Ksp IAP = Ksp IAP < Ksp the excess solute should precipitate out equilibrium condition the solution can dissolve more of the solute Suppose a sample of water contains 5x10-2m of Ca2+ and 7x10-3m of SO42-.58% (c) How can we tell if a given solution is saturated in a particular solute? By determining the Saturation Index (not applicable to hydrolysis reactions.x] = [(5 x 10-2) .negative. assuming that they are numerically equal to activities for very dilute solutions.

7m = solubility of CaF2 Thus. 31 . Solubility of CaF2 = mCa2+ = 1/2 mF– Note that this figure is valid only for CaF2 in contact with pure water containing no Ca2+ or F. Neglecting x2.1+x) (x) = 3. but this is not something we could predict from simple equilibrium reasoning. Experience tells us that x will not be larger than the solubility we calculated for pure water.m2F. x moles of CaSO4 will dissolve in 1 kg of water) The concentration of Ca 2+ in 1 kg of water = x moles (from CaSO4) + 0.. The presence of ions different from those furnished by the salt itself generally increases the solubility.25 x 10-10. but again we will take a short cut for an approximate solution.1 moles (contribution from CaCl2) The concentration of SO42.5.This turns out to be 10-4.4 x 10-5 0. x moles of CaF2 can dissolve in 1 mole of water to make a saturated solution) Since every mole of CaF2 that dissolves gives 1 mole of Ca2+ and 2 moles of F-.4 x 10-5 i.4 x 10-4m [We can and should check the validity of our assumption that x2 is small by back-substitution.in 1 kg of water = x moles/1 kg of water Ksp (CaSO4) = mCa2+ mSO42-= (0. because I have taken the solution of the quadratic equation from Faure.4)1/3 = 10-3.e.4 at 25oC and 1 bar (3.1x.m2F– = (x) (2x)2 = 4x3 = 10-10. 0. hence the term x2 should be small compared to 0. x = 3. Ksp (CaF2) = mCa2+.= 10-10..e.1x + x2 = 3.1x = 3.] The decrease in solubility (compared to pure water) is a result we could have guessed qualitatively by noting that the excess Ca 2+ would speed up the reverse reaction (formation of CaSO4). particularly by an excess of Ca2+ or SO4-2 from other sources? Let x be the solubility of CaSO4 (i.6] (e) What is the solubility of CaF2 in pure water (25oC.e. who uses Ksp (CaSO4) = 10-4. (d) What is the solubility of CaSO4 in a solution of 0. The decrease in the solubility of a salt due to the presence of one of its own ions in solution is called the commonion effect.1m CaCl2? The task here is to find out how is the solubility affected by the presence of other ions in the solution.6. 1 bar)? CaF2 ⇔ Ca2+ + 2FKsp (CaF2)= mCa2+.from other sources.14) Let x be the solubility of CaF2 (i. 1991.4 x = mCa2+ = (0.. instead of 10-4.4 x 10-5 We can solve this quadratic equation for x.

the more soluble mineral is replaced by the less soluble one. 32 . barite will be precipitated.4 x 105 Evidently. Therefore. we can neglect the term 10-10. respectively.25 mSO42. Note: In such situations. barite obviously contributes little to the concentration of SO42-(aq) in the solution. let us calculate the value Keq for the reaction at 25oC and 1 bar Ba2+ + CaSO4 ⇔ Ca2+ + BaSO4 (3.= 3. This replacement anhydrite by barite will go on till the mCa2+ / mBa2+ ratio in the solution approaches the value of Keq.0 x 10-10= 10-10 Keq = mCa2+ / mBa2+ =10 5.4 x 10-5 = 10-4.5 log (mSO42-)2 = log 10-4.5 >> 10-10. That is. as it is much less soluble than anhydrite in the mixture.=1. It means that when a saturated solution of barite comes into contact with anhydrite.5 Ksp(BaSO4) = mBa2+ mSO42.(e) Effect of the solubility of one salt on the solubility of another in the same solution As the last example. and anhydrite will be dissolved in the solution.5 2 log mSO42= -(4. which are common in geology.000 times more than that of Ba2+ in the solution. giving (mSO42-)2 = 10-4. CaSO4 is much more soluble than BaSO4 when the solution is saturated in both. To satisfy the requirement of electrical neutrality: mCa2+ + mBa2+ = (mSO42-) Ksp (BaSO4) + --------------------mSO42- mSO42.15) Keq = mCa2+/ mBa2+ Keq for the above reaction can be calculated from the solubility products of the two component reactions: CaSO4(s) ⇔ Ca2+ (aq) + SO42-(aq) BaSO4(s) ⇔ Ba2+ (aq) + SO42-(aq) Dividing to eliminate mSO42-. the concentration of Ca2+ is 340.5 = 3. How can we calculate solubility of Ca2+ (= mCa2+) and solubility of Ba2+ (= mBa2+)? The obvious technique is to first calculate mSO42We can determine the SO4-2 concentration in the solution by some algebraic manipulation.5 + 10-10 Since 10-4.= K sp(CaSO4) ------------------mSO42- (mSO42-)2 = K sp(CaSO4) + Ksp (BaSO4) = 10-4.25 mole/kg water We can now calculate mCa2+ and mBa2+ using equations for K sp (CaSO4) and Ksp (BaSO4).5) 2log mSO4 = -(4.5) /2 = -2. at which point equilibrium will be restored.= 10-2. Ksp(CaSO4) = mCa2+ mSO42.

t.r. Ar = 0 (Stable w. but is useful for predicting qualitatively which way an equilibrium will shift under different circumstances.16) * Unless mentioned otherwise. Stable: Metastable: Unstable Vr = 0.this is metastability. (2) All the components in each reaction must be expressed in equivalent concentration units. T. but this cannot be predicted from the elementary rules presented here. TIPS FOR PROBLEM SOLVING (1) Make sure that any reaction you are working with is balanced. Ar +ve Vr +ve. solubility increases with increase in temperature (although at different rates for different salts). (3) Where appropriate. THE CONCEPT OF STABILITY The stability of a substance always implies a given set of conditions: P. it pays to be patient and neat. but still continue to exist because the rate of the relevant reaction (Vr) is extremely sluggish -. to equilibrium)* Vr = 0. A substance may actually be unstable in terms of affinity for reaction (Ar). associated substances. make reasonable assumptions for approximate answers (often adequate for your purpose). Le Chatelier's Principle does not help us with any quantitative prediction. Ar +ve (3. (4) Do your work neatly without omitting steps — in the long run. we will use stability in the sense of equilibrium.In general. _____________________________________________________________________________________________ PROBLEM SET 1 — Chemical Equilibrium ______________________________________________________________________________ 33 . LE CHATELIER'S PRINCIPLE A system in equilibrium responds to any disturbance imposed on the system by trying to counteract the effects of this disturbance. How does a system respond to a change in temperature? Through some process that will absorb heat (endothermic reaction) or give off heat (exothermic reaction) How does a system respond to a change in total pressure? Through some process that would produce denser minerals (increase in pressure) or lighter minerals (decrease in pressure). but check the reasonableness of your assumptions.

or oversaturated with respect to the salt. with sketches as necessary] Molality –– Molarity – Mole Fraction Partial Pressure — Dalton’s Law of Partial Pressure Activity – Fugacity Equilibrium (chemical) Law of Mass Action Equilibrium Constant Solubility – Solubility Product Saturation Index Concepts / Applications [should be able to explain these.RECAPITULATION Terms [should be able to define or explain these. Common-ion effect – Solubility of a salt decreases in the presence of one of its own ions in the solution. Calculation of mH2CO3 of water in equilibrium with the atmosphere. saturated. Calculation of solubility under specified conditions. providing justification as necessary] The Solubility Product of a salt can be used to determine if a solution with known dissolved concentration of the salt is undersaturated. 34 . Le Chatelier’s Principle. Stability vs. Metastability Computational Techniques Reasonable approximations for quick approximate solutions of problems.