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ACIDS
You know that acids are sour to taste. You have tasted vinegar, you have also tasted lemon juice which contain acids namely acetic acid and citric acid respectively. Do you know that our gastric juice in the stomach contains hydrochloric acid which is required to digest the carbohydrate food that we eat. Do you know ants contain an acid called formic acid and when ants bite us, we get the pain in our skin due to the the corrosive action of this formic acid? In fact any substance which is sour to taste usually contains an acid. The curd that we eat contains lactic acid. So acids are very important class of compounds which have wide ranging applications. Let us know more about acids. According to Arrehenius theory of acid, substances which can produce H+ in water are called acids.
Types of acids on the basis of strength: When HCl gas is bubbled in water, it undergoes complete dissociation to produce H+ ions and Cl- ions. Nearly all molecules undergo dissociation (ionisation). In other words almost no molecule remains as HCl in the undissociated form. Hence it is called a strong acid. The amount of H+ ions in unit volume of solution is more in such an acid. HCl(gas) -----water------> H+ + Cl - (strongly ionised) (very little) (Very large) But when you put acetic acid in water, all of them will dissolve no doubt but all of them will not ionise. A very little of the acid will undergo dissociation to produce very little of H+ ions. Thus the acid is weakly dissociated and hence is called a weak acid. (weakly ionised) CH3COOH(l) -------water-----> CH3COO - + H+ (very large) (very little) Hence there are two types of acids (a) Strong acids: Acids which are strongly ionised and produce a large number of H+ ions. Examples: HCl(hydrochloric acid) HBr(hydrobromic acid) HI(hydroiodic acid) H2SO4(sulphuric acid) HClO3(chloric acid) HNO3(nitric acid) HClO4(perchloric acid) Relative strength : HI > HBr > HCl = HClO4 > H2SO4 > HNO3 > HClO3 Do you know which acid is the strongest ? it is flouroantimonic acid; HSbF6. (b) Weak Acids: Acids which are weakly ionised and produce a small number of H+ ions Example: HF(hydroflouric acid) HCN(hydrocyanic acid) H2SO3(sulphurous acid) H2CO3(carbonic acid) HNO2(nitrous acid) H3PO4(phosphoric acid more correctly orthophosphoric acid) H3PO3(phosphorous acid or more correctly orthophosphorous acid) H3PO2(hypophosphorous acid) HClO(hypochlorous acid) H3BO3(boric acid or more correctly orthoboric acid) All organic acids: such as HCOOH(formic acid) H2C2O4(oxalic acid) CH3COOH(acetic acid) citric acid, lactic acid and a large number of acids whose formula are beyond the scope of this book. SAQ 1: State TRUE or FALSE. Correct the statement if there is any mistake (i)All acids are not soluble in water. (ii)When an acid dissolves in water, nearly complete ionisation may occur. (iii)Hydroflouric acid is a weak acid. SAQ 2.Indicate which acid is strong and which acid is weak.Also write their formula. sulphuric acid, carbonic acid, nitrous acid, nitric acid, hypochlorous acid, phosphoric acid, sulphurous acid How will you know whether an acid solution is strong acid or weak acid? (i) Electrical conductivity: Since acid solution contains free ions, it conducts electricity. If an electric bulb will be placed
in the electric circuit containing a strong acid solution (say hydrochloric acid), the bulb will glow with intense light as the number of ions produced from strong acid is very large. On the other hand, if the electricity is passed through a weak acid solution(say acetic acid), then the bulb will glow with dim light. This is because the solution contains a small number of ions. (ii) Action on skin: When a strong acid is poured in our skin, it produces painful blisters. The skin colour changes. For example when concentrated nitric acid is poured on our skin, it produces yellow colour colour with painful blister. But when a weak acid is poured in the skin, it is not affected. We eat acetic acid in many dishes in the name of vinegar. It is also used as a preservative to keep food material for a long time without rancidification. But not all weak acids are eatables. HCN is one of the deadliest poison.
Di, tri and tetra protic acids are commonly called polyprotic acids. SAQ 5: Give two examples with names for each of the following (i)oxo acids of sulphur (ii)hydracid of halogen (iii)oxo acids of phosphorous SAQ 6:Give one example of each of a strong and weak oxo acid of sulphur. SAQ 7: Among the following hydra acids which are weak. HCl, HF, HBr, HI, CH3COOH, HCN SAQ 8: Indicate the basicity of each of the following acids H2SO4, HF, H3PO4, HNO3, H3PO3, H2C2O4, H3PO2, HBr SAQ 9: Indicate which of the following are diprotic acids. HCl, H2CO3, H3PO3, CH3COOH, H2C2O4
ACID ANHYDRIDES:
Oxo acids are produced when a nonmetallic oxide reacts with water. For example, when SO3 reacts with water, we get sulphuric acid. SO3 + H2O----------> H2SO4 Hence nonmetallic oxides are called acidic oxides and also called acid anhydrides. The acid anhydrides of the oxoacids are given in Language of Chemistry section. You may revise them now. SAQ10: What are the acid anhydrides of the following oxoacids. H2CO3, HNO3, H3PO4, HClO, HClO4 Hint : Remove all H-atoms in the form of water. If required multiply by the lowest factor to do so.
BASES
Bases are substances which are bitter to taste. Have you tasted raw lime(chuna) while taking a betel? Does it not taste bitter? Bases are the oxides or hydroxides of metals. According to Arrhenius theory base is any substance which produces OH ions in water. A base can react with an acid to produce salt and water. This is called neutralisation reaction. When the reaction takes place, the bitterness of the base and the sourness of the acid no more exist. The product tastes salty and hence is called a salt. Bases are of two types. (i)Metallic oxides (ii)Metallic hydroxides (i) Metallic Oxides: These are the oxides of metals. Examples: Na2O, MgO, CaO, K2O, Al2O3, SnO etc. Note that some of the metallic oxides are amphoteric i.e they can react both with acids and bases to form salt and water. Al2O3 and SnO belong to that category. The details of amphoterism has been discussed in chapter-I. You can revise it now. Some of the metallic oxides are soluble in water. On dissolving in water, they produce their corresponding hydroxides(Chapter-I) Na2O + H2O----------> NaOH Soluble oxides: Alkali metal oxides(Li2O, Na2O, K2O etc) and three oxides of alkaline earth metals such as Ca, Sr and Ba(CaO, SrO and BaO) are soluble in water and form their hydroxides. Others are not. The metal hydroxide solutions are called ALKALI. NaOH and KOH solutions are called alkalis.
Alkalis: The soluble bases consisting of the hydroxides of metals are called alkali. How to test an alkali: (i)It is bitter to taste (ii)It is soapy or slippery to touch. (iii)It turns red litmus blue. SAQ 11: Indicate which oxides are basic and which are amphoteric. Na2O, BaO, K2O, SnO, ZnO, CaO, Al2O3 SAQ 12: Indicate which will form alkali solution. MgO, Na2O, Al2O3, CaO, BeO, K2O, BaO, ZnO SAQ 13: Write the products of the following reactions and what would the resulting solution be called. (ii)MgO+H2O------>? (i) K2O + H2O------->? (iv)Fe2O3 + H2O----->? (iii)BaO + H2O----->? (ii)Metallic hydroxides: The hydroxides of strong metals are bases while hydroxides of semimetals or metalloids are amphoteric. Say for example, NaOH is a base but Al(OH)3 is amphoteric. The hydroxides are characterised by their number of replaceable hydroxy(OH) groups. This is called the (ii) Metallic hydroxides: The hydroxides of strong metals are bases while hydroxides of semi metals or metalloids are amphoteric. Say for example, NaOH is a base but Al(OH)3 is amphoteric. The hydroxides are characterised by their number of replaceable hydroxy(OH) groups. This is called the acidity of the base. The acidity of NaOH is one as it has one replaceable OH group. The acidity of Ca(OH)2 is two and that of Al(OH)3 is three. Metallic hydroxides are solid substances at room temperature. Acidity of a hydroxide base: The number of replaceable OH groups is called acidity of a base. NaOH + HCl -----> NaCl +H2O (here one OH group of NaOH has been replaced by Cl) Ca(OH)2 + 2HCl -----> CaCl2 + 2H2O(here two OH groups of the base have been replaced by Cl) Al(OH)3+ 3HCl -------> AlCl3 + 3 H2O (here three OH groups have been replaced) Solubility: A few hydroxides are soluble in water. These are (i)All alkali metal hydroxides such as NaOH, KOH etc. are soluble in water. (ii)Three alkaline earth metals such as Ca(OH)2, Sr(OH)2 and Ba(OH)2 are soluble in water. The rest hydroxides are insoluble. SAQ 14: Indicate which hydroxide is soluble and which is insoluble in water. NaOH, Zn(OH)2, Ba(OH)2, RbOH, Mg(OH)2, KOH, Be(OH)2, Al(OH)3 Types of alkali on the basis of strength: Some bases are strong because they produce large number of OH- ions when they dissolve in water. Take the case of NaOH solution. Since the solubility of NaOH is very high the concentration of OH- is always very high. Remember that only on dissolution a base undergoes dissociation to produce free metal ion(M+) and hydroxide ion(OH-). Hence whether a base is strong or weak depends on whether it is more soluble or less soluble respectively. Take the case of Ca(OH)2. The solubility of this hydroxide is very low. So the OH- concentration
is low and this is a weak base. Examples of Strong bases: LiOH, NaOH, KOH, RbOH, CsOH, Ba(OH)2 are only regarded as strong bases. Ba(OH)2 is the least strong and CsOH is the strongest among them. The most commonly available strong bases are NaOH and KOH. Other than the above six hydroxides, all metallic hydroxides are weak. The following table gives the solubility of alkali and alkaline earth metal hydroxides: Note that solubility is measured as the number of grams of solute dissolved per 100gm of the solvent to make a saturated solution. Solubility of Some Metallic hydroxides: Hydroxides solubility(gm/100gm) LiOH 12.8 NaOH 109 KOH 112 RbOH 177 CsOH 330
Note from the above table that alkali metal hydroxides are more soluble than alkaline earth metal hydroxides. Be(OH)2 and Mg(OH)2 are almost insoluble. Solubility of hydroxides increases as we move from lower alkali metal to higher alkali metal and so also the same trend is noticed for alkaline earth metal hydroxides. Among alkaline earth metal hydroxides Ba(OH)2 is strongest among alkali metal hydroxides. LiOH is least strong. Alkaline earth metal hydroxides other than Ba(OH)2 have very low solubility and are regarded as weak bases. Note that unlike solubility of acids(all acids are completely soluble whether strong or weak), not all bases are soluble and hence the strength or weakness of a base depends on the solubility. The part of the base which is soluble undergoes ionisation, no doubt, but the weakness results due to poor solubility. The solubility of oxides also follow the same order as hydroxides, although the numerical values are different. SAQ 15: Indicate which are strong and which are weak bases Al(OH)3, KOH, Ca(OH)2, LiOH, Mg(OH)2, Ba(OH)2, SAQ 16: Arrange the following in the order of increasing base strength KOH, LiOH, NaOH, RbOH, Ba(OH)2, Ca(OH)2
SALT
You know that when an acid(sour) reacts with a base or alkali(bitter), we get a salt and water. The salt is salty to taste. I am sure you have tasted the common salt(table salt). How does it taste? That is the taste of all salts. The reaction of sour acid with a bitter base or alkali to produce a salt is called neutralisation reaction. Whether the base is soluble in water(alkali) or not, it reacts with an acid to form salt and water. NaOH + H2SO4 -------> Na2SO4(salt) + H2O HCl + CaO -------> CaCl2(salt) + H2O Al2O3 + HNO3 -------> Al(NO3)3(salt) + H2O In the above three cases, NaOH is completely soluble, CaO is weakly soluble and Al2O3 is insoluble, but all of them reacted with acids to form the corresponding salt and water. SAQ 17: Indicate which salt is produced by the reaction of the following acid and base
(iii)Al(OH)3 + HBr
Types of Salt: There are two three types of salts namely (i)acidic salt (ii)basic salt (iii)basic salt Acidic Salt: Look to the following reaction. H2SO4 + NaOH -------> NaHSO4(acidic salt) + H2O When one mole of sulphuric acid reacts with one mole of sodium hydroxide we find that only one acidic hydrogen atom is replaced from H2SO4 to produce sodium hydrogen sulphate or sodium bisulphate. This salt is an acidic salt because it still contains one acidic hydrogen atom and can react with one extra mole of base(NaOH) to give a normal salt. NaHSO4 + NaOH ------> Na2SO4(normal salt)+ H2O Sodium sulphate has no more acidic hydrogen atom and is called normal salt. So any salt which contains one or more replaceable (acidic) hydrogen atoms is called an acidic salt. Normal Salt: Any salt which does not contain any replaceable(acidic) hydrogen atom is called a normal salt. e.g: K3PO4, MgSO4 etc. SAQ 18: Indicate which one is an acidic salt and which is a normal salt NaHCO3, K2SO4, NaNO3, Na2HPO4, Ca(HSO3)2, KHSO4, Ca(H2PO4)2, NaCl ** (i) Note that a monobasic acid always gives a normal salt. HCl + NaOH -----> NaCl + H2O HNO3 + NaOH------> NaNO3 + H2O CH3COOH + NaOH -----> NaCH3COO(CH3COONa) + H2O All the above salts are normal salts. Note that in sodium acetate, the other 3H atoms are not replaceable. (ii) Dibasic acids form two salts, one acidic salt and the other normal salt. We have seen the case of sulphuric acid in the above example. H2CO3 + NaOH ----> NaHCO3(acidic salt) + H2O NaHCO3 + NaOH -----> Na2CO3(normal salt) +H2O (iii) Tribasic acids give three salts out of which two are acidic and one normal. Take the case of phosphoric acid. H3PO4 + NaOH ------> NaH2PO4(acidic salt: sodium dihydrogen phosphate) + H2O NaH2PO4 + NaOH ---> Na2HPO4(acidic salt: disodium hydrogen phosphate) + H2O Na2HPO4 + NaOH -------> Na3PO4(normal salt: sodium phosphate) + H2O In this case you found that phosphoric acid had three replaceable hydrogen atoms which were replaced one after the other to give two acidic salts and one normal salt. SAQ 19: What salt you will get if you react one mole of H2CO3 with two moles of NaOH? SAQ 20: What salt you get if one mole of sulphurous acid reacts with one mole of NaOH? Is it an acidic or basic salt? What happens when this salt reacts with one mole more of NaOH? SAQ 21:Predict the product and indicate the nature of the salt
(a)NaOH(one mole) + H2S(one mole) ----->? (b)NaOH(one mole) + H3PO3(one mole)------>? (c)NaOH(two mole) + H3PO3(one mole)------->? (d)NaOH(one mole) + H3PO2(one mole)------? (e)NaHSO4 + NaOH ------->? (f)Na2HPO4 + NaOH------->? (g)NaH2PO2 + NaOH------->? SAQ 22: Indicate which one among the following are the normal salts. NaHSO4, Na2CO3, NaH2PO3, Na2HPO3, NaH2PO2, Na2SO4 SAQ 23: Do Na3PO3 and Na2HPO2 exist? Give reason. SAQ 24: Predict the products and indicate the nature of the salt. (i)NaOH(two moles) + H3PO4(one mole)------->? (ii)NaOH(three moles) + H3PO4(one mole)------->? (iii)Na2HPO4 + NaOH ------->? (iv)NaH2PO4 + NaOH(one mole) ------>? (v)NaH2PO4 + NaOH(two moles)------>? SAQ 25: Indicate which one is acidic salt and which normal salt. Write their formula. calcium nitrate, Aluminium chloride, Magnesium hydrogen sulphate, Potassium bicarbonate, Ferric sulphate, Sodium hypophoshite, calcium dihydrogen phsophate, Sodium dihydrogen phosphate, Potassium bromide, Magnesium bisulphite, Disodium hydrogen phosphate SAQ 26: How many salts H4P2O7 will form? Write all of their sodium salts.
Basic Salt:
If a base contains one replaceable OH group it will form a normal salt after reacting with one mole of an acid. NaOH + HCl ------> NaCl + H2O But if the base contains more than one OH groups and only one of them is replaced by one mole of an acid and other remains in the salt, such a salt will be called a basic salt. It can further react with one mole more of acid to produce the normal salt. Mg(OH)2 + HCl ------> Mg(OH)Cl(basic salt) + H2O Mg(OH)Cl + HCl -------> MgCl2(normal salt) + H2O SAQ 27: What salts will be obtained in the following reactions (i)one mole of Fe(OH)3 + one mole of HCl ------->? (ii)One mole of Fe(OH)3 + two moles of HCl------->? (iii)One mole of Fe(OH)3 + three moles of HCl ------->? SAQ 28: Indicate which one of the following are acidic, normal and basic salts K3PO4, Mn(OH)Br, NaHCO3, NaH2PO2, K2HPO3, KHPO4, Mg(NO3)2, NaHS, CH3COOK
HYDROLYSIS OF SALT
It is a general belief that an acid solution is acidic, a base(or alkali) solution is basic(or alkaline) and a salt solution is neutral. More clearly speaking, an acid turns blue litmus red, an alkali turns red litmus blue while the salt which is produced by the neutralisation reaction of an acid and a base is neutral. This is not really true. A salt solution may or may not be neutral. Let us prepare three salt solutions in three different test tubes, one containing NaCl, other containing NaCN and the third containing NH4Cl. Let us try with litmus papers. We shall find that while NaCl solution will be neutral(no litmus paper will change colour), NaCN
solution will be alkaline(red litmus will turn blue) and NH4Cl solution will be acidic(blue litmus will turn red). This is due to a phenomenon called hydrolysis of salt. The salt reacts with water to a small extent(partially) and produces either excess of H+ ions or OH- ions and makes the solution acidic or basic respectively. On the basis of nature of hydrolysis, salts are of four types. (A) Salt of strong base and weak acid: We know that the common strong bases are NaOH and KOH. Almost all other bases are weak. The strong acids are also few in number. They are H2SO4, HNO3, HCl, HBr, HI, HClO3 and HClO4. All the remaining acids fall under weak acid category. Salt containing Na+ or K+ as basic radical and any acid radical other than SO42-, NO3-, Cl-, Br -, I-, ClO3- and ClO4- is called a salt of strong base and weak acid. In other words, they have been prepared by the reaction of a strong base NaOH or KOH and weak acid other than H2SO4, HNO3, HCl, HBr, HI, HClO3 and HClO4. Such a salt when dissolved in water produces basic or alkaline solution. This is due to partial hydrolysis of the salt. Examples: NaCN, K3PO4, KNO2, NaCH3COO(CH3COONa) etc. NaOH(aq) + HCN(aq) NaCN(aq) + H2O(l) strong weak + + Na + OH- + HCN Total ionic equation: Na + CN + H2O(l) Note that NaOH is a strong electrolyte(strong base) and almost completely dissociates into ions, while HCN is a weak electrolyte(weak acid) and is almost non-ionised. So it has been kept as such. If we cancel the spectator ions from both the sides(Na+), we get, OH- + HCN Net Ionic equation: CN- + H2O Due to presence of excess OH- ions as shown above, the solution becomes alkaline. Note that salts of this type which has Na+ and K+ as basic radical and any acid radical other than the seven given before behave in the same way as NaCN i.e produce alkaline(basic)solution. SAQ 29: Which of the following solutions will be alkaline to litmus. (ii)Na2CO3 (iii)FeCl3 (i)KNO2 (v)Na2SO4
(iv)CuSO4
(B) Salt of strong acid and weak base: This type of salt contains basic radical other than Na+ and K+ and acid radical one of SO42-, NO3-, Cl-, Br-, I-, ClO3- and ClO4-. In other words they have been prepared by the reaction of a weak base i.e any base other than NaOH and KOH and strong acids, i.e one of H2SO4, HNO3, HCl, HBr, HI, HClO3 and HClO4. Such a salt when dissolved in water forms an acidic solution due to partial hydrolysis. CuSO4, Zn(NO3)2, NH4Cl etc. Examples: MgCl2, NH4OH(aq) + HCl(aq) NH4Cl(aq) + H2O(l) weak strong While NH4OH is a weak base and remain mostly non-ionised, HCl is a strong acid and will ionise almost completely to form H+ and Cl- ions. The total ionic equation would be NH4OH + H+ + ClTotal Ionic Equation: NH4+ + Cl- + H2O Cancelling the spectator ion(Cl ), we get the net ionic equation, NH4OH + H+ Net Ionic Equation: NH4+ + H2O
Due to the presence of excess H+ ions, the solution behaves acidic. Salts of NH4Cl type as given before behave in the same manner and produce acidic aqueous solution. SAQ 30: Indicate which salt will form acidic solution and why? (ii)Al(NO3)3 (iii)MgBr2 (iv)Na2SO4 (i)K2CO3 (v)FeSO4 (C) Salt of Weak acid and weak base: Salt which contains basic radical other than Na+ and K+ and acid radical other than SO42-, NO3-, Cl-, Br-, I-, ClO3- and ClO4- fall into this category. Such salt solution is nearly neutral because they produce nearly same quantity of H+ and OH- ions. Example: NH4CN, Al(NO2)3, MgF2, CuCN,(NH 4)CH 3COO[CH3COONH4] etc. NH4OH(aq) + HCN(aq) NH4CN(aq) + H2O(l) Both NH4OH and HCN are weak electrolytes and remain mostly in non-ionised state. NH4OH + HCN Total ionic equation: NH4+ + CN- + H2O weak weak So H+ and OH- ions remain in nearly equal amounts due to their weak dissociation. Thus the solution is nearly neutral.The salt may be slightly acidic or alkaline depending on whether the weak acid is relatively stronger or the weak base is relatively stronger. SAQ 31: Indicate which of the salt solution is nearly neutral and why? (ii)NH4F (iii)FePO4 (iv)Ca(NO3)2 (i)Na2SO3 (D) Salt of strong acid and strong base: Salt which contain either Na+ or K+ as basic radical and one of SO42-, NO3-, Cl-, Br-, I-, ClO3and ClO4- as acid radical belongs to this category. Aqueous solution of such a salt is neutral because it produces equal amounts of H+ and OH-. Example: NaCl, KNO3, Na2SO4, KBr etc. NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l) strong strong Both the acid and base formed due to hydrolysis are strong and dissociates completely. Thus H+ and OH- concentrations remain same and the solution is neutral. Na+ + OH- + H+ + ClTotal Ionic equation: Na+ + Cl- + H2O Cancelling the spectator ions, we get H+ + OHNet Ionic equation: H2O SAQ 32: Indicate which one of the following shall give neutral solution. (ii)CuSO4 (ii)KCN (iv)NaI (i)K2SO4 (v)NH4Cl SAQ 33: Indicate which salt will produce neutral(N), nearly neutral(NN), acidic(A) and basic(B) solutions. (iii)(NH4)2SO4 (iv)K2SO3 (v)NH 4NO2 (i)NaBr (ii)MgBr2 (vi)CuBr2 (vii)KNO3 (viii)AlF3 (ix)Na2C2O4(sodium oxalate) (x)Potassim acetate
BRONSTED-LOWRY THEORY
Acids : Any substance which can accept a H+ ion is called an acid. (PROTON DONORS) Examples: (i) All inorganic and organic acids discussed before (ii) NH4+ (ammonium ion) and H3O+ (hydronium ion) Bases: Any substance which can accept a H+. (PROTON ACCEPTORS) Bronsted bases are of two types. (i) all negative ions : e.g Cl, OH, SO42, CH3COO , NO3 etc. (ii) neutral molecules in which the central atom carries a lone pair. e.g H2O, NH3, C2H5OH etc. One lone pair on N and two lone pairs on O are not shown here. ACID-BASE REACTION: The acids show their acidic properties in water by reacting with it. Hence the dissolution of acid in water is not a physical change as suggested by Arrhenius theory rather it a chemical change i.e an acid-base reaction.
In the forward reaction, HCl loses a proton and H2O accepts it hence the former is acid and latter is base. In the backward reaction, H3O+ loses a proton and Cl accepts it, hence the former is the acid and latter is the base. Since HCl is a strong acid the equilibrium lies almost entirely to the right. In other words, HCl is almost fully ionised and the reactionis virtually irreversible. If you have little idea about reversible reactions and concept of equilibrium then read the chapter chemical equilibrium. Note that we commonly write H+ in stead of H3O+.
CH3COOH Acid-1
+ H2O Base-1
In this case, CH3COOH(acetic acid) is a weak acid and the equilbrium lies far to the left. In other words the acid dissociates into ions to a small extent and most of the acid remains unionised. In both the above examples H2O acts as base in the forward process and H3O+ acts as an acid in the backward process.
In this case, NH3 accepts a proton and H2O loses it in the forward reaction, hence H2O acts as acid and NH3 as base. In the backward reaction, NH4+ loses a proton and OH accepts it,
hence the former is an acid and latter a base. Note that in the earlier examples H2O acted as a base while in the above example, it acts as an acid. Therefore water has ampoteric property. Since NH3 is a weak base, the equilbrium lies far to the left, i.e the dissociation into ions is small.
CONJUGATE ACID-BASE :
Two species which differ from each other by a single H+ ion is called a conjugate acid-base pair. Example: HCl/Cl : HCl is the acid and Cl is its conjugate base. NH3/NH4+ : NH3 is the base and NH4+ is its conjugate base. In fact, each is the conjugate of the other. Other examples : H2O/H3O+; H2O/OH, NH3/NH2; CH3COOH/CH3COO, H2SO4/HSO4 SAQ 37 : Give the conjugate bases of the following acids. (a) HSO4 (b) H3PO4 (c) HPO 42 (d) NH4+ (e)H 2O SAQ 38 : Give the cojugate acids of the following bases. (a) H2PO 4 (b)CN (c) HCO3 (d) NH2 (d) OH
In other words, HF is the weakest acid and HI is the strongest acid. Therefore F is the strongest base while I is the weakest base. Note that this concept is applicable in a relative basis for the sake of comparison. The acid or base may or may not be really strong or weak according to the actual meaning of strong or weak acids. SAQ 39 : If the acid strength order of four acids is HCl > CH3COOH > H2CO3 > HCN, then what is the base strength order. SAQ 40: (a) Why CO2 produces H+ when dissolved in water ? (b) Why Cl, NO3-, HSO4- are weak bases ?
HA
A
-
KA =
H A HA
Where KA is the dissociation constant of the acid. The molarities of H+ and A ion multiplied in the numerator while the molarity of undissociated HA is in the denominator. Already it has been told that essentially all reactions reversible but practically many are irreversible. If HA is HCl/HBr/HI, it is irreversible and almost negligible undissociated HA(LHS) remains at equilbrium. Hence in such cases, KA is very large. In fact if KA of a acid is above 10, it is regarded as strong acid. Often this value is more than 105 for strong acids. But if the acid is weak like HF or HCN, then the numerator values are small while the denominator value is large. Hence KA is very small. For example the KA for HCN is 4.8 X 108. From such a small value you can well imagine how small would be the concentration of H+ ion in solution. Base Dissociation: A Bronsted base produces OH by reacting with water.
NH3 + H2 O
+ NH4 + OH
For LHS, we commonly write NH4OH in stead of NH3 + H2O. The base dissciation constant, KB is written as follows.
K =
B
NH4 OH NH4OH
= 1.8 X 105
Since NH3(NH4OH) is a weak base, the base dissociation constant is too small. You can well imagine how small is the concentration of OH . IMPORTANT : OH, NH2 and H are strong bases and the rest of bases are weak. KB value of OH is not written as the cause of basicity of a base is the presence of OH. Weak bases have low KB values while strong bases have high KB values. SAQ 41 : Give the dissociation equation for CN in water and write the expression of KB. SAQ 42 : Indicate which one is strong and which one weak acid or base according to Bronsted theory. NH3, OH, H2O, Cl, NH2, H2SO4, HCl SAQ 43 : Give the acid dissociation equation for H2SO4 and write the expression of KA.
H2 O + H2 O
H2O
H + OH
KW = [H ] X [OH ]
KW is called the ionic product of water which is constant at a given temperature. Note that molarity of H2O has been deleted from the denominator as it is constant. 14 0 W At room temperature, the product of the molarities of H+ and OH is constant and is so low. From this value, you can well imagine to what small extent water is dissociated into ions. Note that whether the solution is pure water, or a neutral solution or acid or basic solution, this product is constant. If one increases the other has to decrease. PURE WATER OR NEUTRAL SOLUTION: In this case, [H+] = [OH]. So [H+]2 = 1014; [H+] = [OH] = 107 mol/L(M) In other words, in one litre pure water or a neutral solution, only 107 mole of H+ and 107 mole of OH are present. ACIDIC SOLUTION: If the solution is acidic then [H+] > 107 and hence [OH] < 107 [H+] > [OH] Note that the product of two concentration is 1014. Example: If a certain acid has [H+] = 104M, then what is its [OH] ? Answer : 1014/104 = 1010
K = 10
(25 C)
BASIC SOLUTION : If the solution is basic or alkaline then [OH] > 107, hence [H+] < 107. [H+] < [OH] Example : A certain base has [OH] = 103M, what is its [H+] ? Answer : [H+] = 1014/103 = 1011
pH SCALE :
From the above discuss we knew that every solution, be it acidic, basic or neutral, has [H+] as well as [OH]. In stead of expressing hydrogen and hydroxyl concentrations for very dilute solutions as a -ve power of 10, it can be expressed by a simple numerical like 3, 4, 5.6 etc. P.L Sorrensen introduced the pH scale.
Weak Acids:
HX
H A HA +
H + X
KA =
[H ] HA
+ 2
= KA [HA]
Note that here we have made an assumption that concentration of HA at equilibrium is same as the initial HA concentration. This is justified becaue the degree of dissocation is very small in such substances at moderate concentrations. But if the solution is diluted, the degree of dissociation is appreciably large and HA concentration at equilbrium wll be less than the initial HA concentration. Hence the above method will fail to determine the correct [H+}. We stop further discussion on this topic and keep it pending for higher study. Same method will be used to determine OH concentration of a weak base like NH4OH. SAQ 47 : Determine the pH of (i) 0.1M CH3COOH having KA = 1.8 X 105) Relative Acid Strength for Weak Acids: From the KA values, the decreasing acid strength of a few weak acids is given below. At a fixed concentration of acid, the [H+] remain in the decreasing order in this case.
H2SO3 > H3PO4 > HF > HNO2 > CH3COOH > H2CO3 > H2S > HCN > H2O
Determination of pH by pH Paper:
The approximate pH of various solutions can be determined by using pH paper. pH paper tiny booklets are availale in chemical stores. The cover page of this booklet gives different colours with the corresponding pH range. A pH paper is plucked out of the booklet and dipped into a solution. A certain colour develops on the paper. The paper is then dried and colour developed on it is compared with the colour given in the cover page of the booklet to determine the approximate pH range such as 02, 24, 8 10 etc. Preparation of pH Paper : Red cabbage or red onion or red hibiscus flower is cut into small pieces and then boiled in water for a long time till the aq. solution gets a deep violet color or blood red colour. Then the solution is filtered to reject the residue. Small pieces of filterpapers are impregnated with this coloured solution, then heated and dried. Now the pH paper is ready for use. It contains a dye named as flavin which gives various colours at different [H+] hence pH. In acid solutions, the pH paper gives red colours while in basic solution it gives various types of blue colour. pH range of some common solutions are given below.
Solution HCl(10M) Lead Storage Battery Gastric juice Lemon juice Cola(Coca cola/pepsi) Vinegar Orange/Apple juice Beer Acid rain Human urine Coffee
Solution Tea Skin of healthy man Milk Pure Water Saliva of healthy man Blood Soap(bath) Household ammonia Caustic soda
RESPONSE to SAQs
SAQ 1:(i)FALSE: All acids are soluble in water. (ii)FALSE: When an acid dissolved in water partial(for weak acid) or nearly complete(for strong acids) dissociation occurs. (iii)TRUE SAQ 2: H2SO4: Strong; H2CO3: Weak; HNO2: Weak; HNO3: Strong; HOCl: Weak; H3PO4: Weak; H2SO3: Weak. SAQ 3: (i)Strong (ii)diluted strong (iii)weak (iv)concentrated weak (v)concentrated strong (vi)diluted weak SAQ 4: All of them are soluble in water. SAQ 5: (i) H2SO4(sulphuric acid) H2SO3(sulphurous acid) (ii)HCl(hydrochloric acid), HBr (hydrobromic acid) (iii)H3PO4(phosphoric acid), H3PO3(phosphorous acid) Weak: H2SO3(sulphurous acid) SAQ 6: Strong: H2SO4(sulphuric acid); SAQ 7: Weak: HF, HCN (Note that CH3COOH although is weak acid is an oxoacid) SAQ 8: H2SO4: 2, HF:1, H3PO4:3, HNO3:1, H3PO3: 2, H2C2O4:2, H3PO2:1, HBr:1 SAQ 9: H2CO3, H3PO3, H2C2O 4 SAQ 10: CO2, N2O5, P2O5(P4O10), Cl2O, Cl2O7 SAQ 11: Basic: Na2O, BaO, K2O, CaO Amphoteric: SnO, ZnO, Al2O3 SAQ 12: Alkali: Na2O, CaO, K2O, BaO (Other oxides are not soluble in water) (iv)Not SAQ 13: (i)KOH (ii)Not soluble(no reaction) (iii)Ba(OH)2 soluble (i) and (iii) solutions are called alkalis as these are soluble hydroxides. RbOH, SAQ 14: Soluble: NaOH, Ba(OH)2, KOH, Insoluble: Zn(OH)2, Mg(OH)2, Be(OH)2, Al(OH)3 SAQ 15: Strong: KOH, LiOH, Ba(OH)2, Weak: Al(OH)3, , Ca(OH)2, , Mg(OH)2, SAQ 16: Ca(OH)2<Ba(OH)2<LiOH<NaOH<KOH<RbOH (Refer solubility table) (ii)FeSO4 (iii)AlBr3 (iv)FePO4 SAQ 17: (i)Na3PO4 (v)Mg(NO3)2 SAQ 18: Normal: K2SO4, NaNO3, NaCl Acidic salt: NaHCO3, Na2HPO4, Ca(HSO3)2, KHSO4, Ca(H2PO4)2
SAQ 19: H2CO3 + 2NaOH --------> Na2CO3(normal salt) +2H2O SAQ 20: H2SO3 + NaOH ---------> NaHSO3(sodium bisulphite) + H2O It is an acidic salt. It forms narmal salt when it reacts with one mole of NaOH NaHSO3 + NaOH -------> Na2SO3(normal) + H2O SAQ 21: Predict the product and indicate the nature of the salt (a)NaHS(acidic salt) (b)NaH2PO3(acidic salt) H3PO3 is dibasic) (c)Na2HPO3(normal salt as (d)NaH2PO2(normal salt as H3PO2 is monobasic) (f)Na3PO4(normal)+ H2O (e)Na2SO4(normal) + H2O (g)No reaction: as it is a normal salt SAQ 22: Na2CO3, Na2HPO3, NaH2PO2, Na2SO4 SAQ 23: No, Na3PO3 and Na2HPO2 do not exist? H3PO3 is a dibasic acid and maximum two H atoms can be replaced while H3PO2 is a monobasic acid and maximum one H atom can be replaced. (ii)Na3PO4(normal) (iii)Na3PO4(normal) SAQ 24: (i)Na2HPO4(acid salt) (v)Na3PO4(narmal) (iv)Na2HPO4(acid salt) KHCO3:acid; SAQ 25: Ca(NO3)2: normal; AlCl3: normal; Mg(HSO4)2:acidic; NaH2PO2:normal, Ca(H2PO4)2: acidic; NaH2PO4:acidic; Fe2(SO4)3:normal; Na2HPO4:acidic. KBr:normal; Mg(HSO3)2:acidic; SAQ 26: Four salts can be formed from H4P2O7. They are Na3HP2O7, Na2H2P2O7, NaH3P2O7 and Na4P2O7.. (ii)Fe(OH)Cl2(basic salt) SAQ 27: (i) Fe(OH)2Cl (basic salt), (iii)FeCl3(normal salt) SAQ 28: acidic: NaHCO3, KHPO4, NaHS, normal: K3PO4, NaH2PO2, K2HPO3, basic: Mn(OH)Br Mg(NO3)2, CH3COOK; SAQ 29: (i)KNO2(salt of strong base KOH and weak acid, HNO2) (ii)Na2CO3(salt of strong base NaOH and weak acid, H2CO3) SAQ 30: (ii)Al(NO3)2: It is salt of weak base Al(OH)3 and strong acid HNO3 (iii)MgBr2: It is a salt of weak base Mg(OH)2 and strong acid HBr (v)FeSO4: It is a salt of weak base Fe(OH)2 and strong acid H2SO4. SAQ 31:` (ii)NH4F: It is a salt of weak base NH4OH and weak acid HF (iii)FePO4: it is a salt of weak base Fe(OH)3 and weak acid H3PO4 SAQ 32: (i)K2SO4: It is a salt of strong base KOH and strong acid H2SO4 (iv)NaI: It is a salt of strong base NaOH and strong acid HI SAQ 33: (i)N(salt of strong base NaOH and strong acid HBr) (ii)A:salt of weak base Mg(OH)2 and strong acid HBr (iii)A: salt of weak base NH4OH and strong acid H2SO4 (iv)B: salt of strong base KOH and weak acid H2SO3 (v)NN: salt of weak base NH4OH and weak acid HNO2 (vi)A: salt of weak base Cu(OH)2 and strong acid HBr (vii)N: salt of strong base KOH and strong acid HNO3 (viii)NN: salt of weak base Al(OH)3 and weak acid HF (ix)B:salt of strong base NaOH and weak acid, H2C2O4(oxalic acid), (x)KCH3COO(CH3COOK): B: salt of strong base KOH and weak acid, CH3COOH(acetic acid).
SAQ 34: (i)No, HCl can not donate H+ ion to acetone or benzene, hence its acid property is not shown. (ii)No, it is not a chemical process. It is a physical change i.e separation into hydrated ions. NaOH(s) + aq. Na+(aq.) + OH(aq.) + (iii) The actual acid in such case H3O . (iv) Undissociated NH3 molecules exist in large quantity while NH4+ and OH exist in small quanitities. Hence there is no existence of NH4OH molecule which we often write as a matter of practice for NH3+H2O (v) Yes, NH3 gas reacts with HCl gas in the vapour state to form dense white fumes of NH4Cl. No water is required for this reaction. Proton transfer occurs in the vapour state too. According to Arrhenius theory, NH3 is a base only in aq. solution, which is not true. Water is not always required for a base to show its properties. (vi) Common bases like NaOH, Ca(OH)2 etc. produce free OH in aq. solution. But a base can directly react with an acid without producing OH like the example of NH3 given in the previous question. SAQ 35 : (a) BB (b) BA (c) BB (d) BA (e) BB/BB(both) (f) BB/BB(both) (g) BB/BB(both) (h) BA (i) BB/BB(both) (j) H3O+ SAQ 36 : (a) NH3(aq.) produces small quantity of OH in water and HCl produces large amount of H3O+ in water. These two ions react with each other to form two H2O molecules. Thus the equilbrium for the NH3 reaction with H2O giving OH is driven more and more to the right till the reaction is complete. (b) Similar to the above reaction. SAQ 37 : (a) SO42 (b) H2PO4 (c) PO 43 (d) NH3 (e) OH SAQ 38 :(a) H3PO4 (b) HCN (c) H2CO3 (d) NH3 (d) H2O SAQ 39 : Cl < CH3COO < HCO3 < CN SAQ 40 :(a) CO2 forms carbonic acid(H2CO3) when dissolved in water. This acid dissociates to from H+ and HCO3. (b) Because HCl, HNO3 and H2SO4 are strong acids. SAQ 41 :
-
CN + H2 O
HCN + OH
K =
B
HCN OHCN
Note that the molarity of H2O is not written as it is a constant quantity. SAQ 42 Strong acids : H2SO4 and HCl Weak acids : NH3, H2O Weak bases : NH3, H2O, Cl Strong bases : OH, NH2 SAQ 43: H2SO 4
HSO 4
+ H2O
+ H3 O
+ HSO4 H KA = H2SO4
SAQ 44 : Less the pH more is the acid strength i.e more is the H+ ion concentration. More the pH more is the base stregnth i.e more is the OH concentration. For example, an acid having pH=3 has [H+] = 103 has more H+ concentration than another acid having pH = 4 i.e [H+]=
104. Similarly a base having pH = 11 has [H+] = 1011 and [OH] = 103 has more OH concentration than another base having pH = 10 i.e [OH] = 104. SAQ 45 : (a) [H+] = 3 X 103; pH = log (3 X 10-3} = -log3 + 3 = 0.477 + 3 = 2.523 [OH ] = 1014/(3X103) = 3.33 X 1012 M (b) [H+] = 2 [H2SO4} = 2 X 0.04 = 0.08; pH = -log(8X102) = log23 +2 = 3log2 +2 = -3 X 0.301 + 2 = 1.097 (because one H2SO4 molecule produces 2 H+ ions) 14 -2 [OH ] = 10 /(8X10 ) = 1.25 X 1013M SAQ 46 : (a) [OH] = 2 X 104; pOH = -log(2X104) = -0.301+4 = 3.699 Hence pH = 14 3.699 = 10.301 [H+] = 1014/(2X104) = 5 X 1011M You can get pH from [H+] as usual also. (b) [OH ] = 2 X 0.04 = 0.08M. Then find pOH as usual and then pH by substracting the pOH from 14. Or else first find [H + ] and then find pH. SAQ 47 :
+ H = KA [HA] = 1.8 X 10-5 X 0.1
-3 = 1.34 X 10
pH = -log(1.34 X 103) = - log 1.34 +3 = 0.127 + 3 = 2.873 (Note that had the acid been HCl, then the pH would have been log 101 = 1. In this case the pH is geater because [H+] is lower.