HARPIC

Like many products, Harpic is a brand, rather than a single product. The brand covers a range of products associated with cleaning and killing germs in and around the lavatory bowl. This article will concentrate on the core product, Harpic limescale remover.

Figure 1: Harpic limescale remover

What is limescale? Limescale is a hard, whitish, chalky deposit found inside kettles and also around taps, sinks and toilet bowls. t is formed when dissolved salts present in hard water come out of solution as the water evaporates. ! ma"or component is calcium carbonate which comes from limestone. #hen rainwater seeps through limestone rock on its way to a reservoir, it dissolves some of it. This is the origin of limestone caves. Limestone is mainly calcium carbonate, which is almost insoluble in pure water, but rainwater naturally contains dissolved carbon dio$ide which makes it acidic. The following reaction occurs, dissolving limestone as calcium hydrogencarbonate %calcium bicarbonate& and so calcium and hydrogencarbonate ions are present dissolved in tapwater ' see (algon. (a()*%s& + H,)%l& + (),%a-& (a,+%a-& + ,H()*'%a-& .H 've

! similar reaction can occur with magnesium carbonate. /otice that rainwater is naturally acidic because of dissolved carbon dio$ide, which is normally present in the air and takes part in the e-uilibria0 H,)%l& + (),%a-& H()*'%a-& + H+%a-& H,()*%a-&

Acid rain
!t the present time, rainwater is becoming more acidic due to the activities of mankind0 the burning fossil fuels, which are carbon'based compounds, is increasing the level of carbon dio$ide in the air1

burning the sulfur'containing impurities present in many fossil fuels leads to sulfur dio$ide which is o$idised to sulfur trio$ide and then converted to sulfuric acid in the atmosphere1 high temperature combustion processes combine o$ygen and nitrogen from the air to form nitrogen o$ides which then react with water to form nitric acid.

Figure 2: E ect o acid rain on trees

!uestion 1 Write "alanced e#uations to sho$ ho$ a% sul ur "urns in o&'gen to orm sul ur dio&ide "% reacts $ith urther o&'gen to orm sul ur trio&ide c% ho$ sul ur trio&ide reacts $ith $ater in the atmosphere to orm sul uric acid !s the water evaporates, the e-uilibrium (a()*%s& + H,)%l& + (),%a-& (a,+%a-& + ,H()*'%a-& 2H 3ve

moves to the left to deposit calcium carbonate ' limescale. !uestion 2 (uggest t$o reasons $h' limescale tends to orm more around the hot tap than the cold tap in a "athroom sin)*

+issolving limescale ,1 o 2%
(alcium carbonate is virtually insoluble in water but dissolves readily in acids. 4trictly it is reacting with them rather than simply dissolving. Harpic contains hydrochloric acid which dissolves limescale, calcium carbonate %(a()*&, as shown.

(a()*%s& + ,H(l%a-&

(a(l,%a-& + (),%g& + H,)%l&

Hydrochloric acid is a strong acid which means that it dissociates completely into ions0 H(l%a-& H+%a-& + (l'%a-&

!uestion H'drochloric acid is a solution o h'drogen chloride gas* a% Wor) out the volume ,at room conditions% o h'drogen chloride dissolved in 1 dm- Harpic* "% Wor) out the mass o h'drogen chloride dissolved in 1 dmHarpic* The concentration of H(l in Harpic is around 567, which e-uates to appro$imately * mol dm'*. !uestion . Calculate /HCl0 to produce a pH o 1 )ther acids that are sometimes used in products for removing limescale are the weak acids sulfamic acid %4)*H/H,&, formic acid %H())H& and phosphoric acid %H*8)9&, :igure *. #eak acids dissociate only partly in solution.

sul amic acid

ormic acid

phosphoric acid Figure -: (tructures o sul amic2 ormic and phosphoric acids

!uestion 3 What is the s'stematic name o

ormic acid?

The strength of a weak acid is measured by its pKa value 0 4ulfamic acid %H)4),/H,& pKa ; 6.<< :ormic acid %H())H& pKa ; *.=

8hosphoric acid %H*8)9& pKa5 ; ,.51 pKa, ; >.,6 1 pKa* ; 5,.*= pKa value is a measure of how easily a H+ ion is lost. The larger the pKa value, the weaker the acid.

+issolving limescale ,2 o 2%
magine a weak acid H! which dissociates H!%a-& H+%a-& + !'%a-&

The e-uilibrium constant is given by0 Kc ;

[H + (aq) ] eqm [A (aq) ] eqm [HA (aq) ] eqm

:or a weak acid, this is usually given the symbol Ka and called the acid dissociation constant* Ka ;
[H + (aq) ] eqm [A (aq) ] eqm [HA (aq) ] eqm

The pKa is defined as follows and is analogous with pH ;'log56?H+@0 pKa 4 5 log11Ka !uestion 6 Calculate the pH o a 1 mol dm7- solution o sul amic acid* The larger the value of Ka, the stronger the acid i.e. the greater ?H+@ it produces on dissociation. However, because of the negative sign in the e$pression above, the larger the value of pKa, the weaker the acid. !uestion 8 a% E&plain $h'2 $hen ormic acid dissociates2 the h'drogen atom "onded to an o&'gen is the one lost as a H9 ion rather than the one "onded to the car"on atom* "%:he pKa o ormic acid is -*;2 $hat is the value o Ka? <ive the correct units c% Write an e&pression or Ka o ormic acid ,represent the acid as HC==H% d% Calculate the pH o a 1 mol dm7- solution o ormic acid* e% Compare 'our ans$er or the pH o ormic acid $ith that o 1 mol dm7- h'drochloric acid ,HCl%2 a strong acid* Ho$ much limescale $ill Harpic dissolve?

(a()*%s& + ,H(l%a-& 5 mol , mol

(a(l,%a-& + H,)%l& + (),%g&

(onsider a typical dose of Harpic is appro$imately A6 cm*. Boles H(l ;

C xV 1 x 50 ; ; 6.6A mol 1000 1000

This will dissolve half this i.e 6.6,A mol (a()* Mr (a()* ; 566 g mol'5 4o the Harpic will dissolve ,.A g calcium carbonate.

>i&ing acid7"ased and "leach7"ased cleaners

! number of other household cleaners such as (illit Cang Toilet (leaner are formulated with a chlorine'based bleach. These are essentially solutions of chlorine in alkali in which the following e-uilibrium is set up. (l,%g& + )H'%a-& H(l)%a-& + (l'%a-&

The active bleaching agent is H(l)%a-&, chloric% & acid. t is important not to mi$ chlorine'based and acid'based cleaners %of any brand& and there are warnings to this effect on the bottles. )n adding acid to bleach, the added acid will react with the )H' ions to form water and, by Le (hateliers principle, the e-uilibrium above will move to the left, with the conse-uent formation of poisonous chlorine gas. /ot a good ideaD n other words, the reaction H(l)%a-& + H(l%a-& goes essentially to completion. !uestion ; A similar product to Harpic states on the pac) ?this uni#ue ormula sho$s 'ou $here it is $or)ing "' turning rom green to "lue and i@@ing on contact $ith limescaleA* E&plain the i@@ing and sggest ho$ the colour change ma' "e "rought a"out* !uestion B Calculate ho$ much chlorine could "e produced rom a t'pical dose o Harpic o 31 cm- assuming that there $as e&cess "leach* ! reference database on chemical haEards, (LF!844 HaEcards, gives the following information about chlorine0 To$ic by inhalation. rritating to eyes, respiratory system and skin. #FL 5.A mg m'* %4TFL& Let us put this in conte$t. #FL stands for #orkplace F$posure Limit and is the ma$imum concentration to which workers may be e$posed by (l,%g& + H,)%l&

breathing, and 4TFL stands for 4hort Term F$posure Limit, i.e. an e$posure for 5A minutes. magine a smallish bathroom , m $ , m $ * m. This gives a volume of 5, m*. This gives an average chlorine concentration of *AA6 G 5, ; ,<H mg m' * . This is well above the -uoted level of 5.A mg m'* for a 5A minute e$posure. 4o this poses a significant problem. Let us check our assumptions and conditions Bany bathrooms will be larger than the e$ample given, thus reducing the concentration of chlorine Cathrooms are normally well'ventilated %often with a fan&, so the chlorine would dissipate. Bost people will not spend as long as 5A minutes in the room after cleaning the toilet. The smell of chlorine will alert people to the danger. (hlorine is denser than air and so will tend to remain in the toilet bowl rather than spreading throughout the room. (hlorine is fairly soluble so some of it would remain dissolved in the water in the toilet.

However, this is clearly not a good idea, and care should be taken not to mi$ bleach and acid'based cleaners. n particular, people with breathing problems such as asthma might be more severely affected.

=ther ingredients ,1 o 2%
Harpic is not "ust a solution of hydrochloric acid. The ingredients of Harpic 5667 limescale remover original are listed in :igure * in decreasing order of -uantity.

Figure -: Ingredients o Harpic 111C limescale remover original

!-ua means water. 8arfum and colour do as their name suggests and make the product pleasant to use. )f the other ingredients, 8FI', hydrogenated tallow ammonium chloride, tallowtrimonium chloride and laureth'56 are detergents or surfactants. These are tadpole'shaped molecules, that is they have a polar or ionic head which will mi$ readily with water and a non'polar tail There is strong hydrogen bonding between water molecules which forms a skin %known as surface tension& at the surface of water and tends to pull it into droplets, :igure 9. 4urfactant molecules, as the name implies, cluster at the water surface with heads in the water and tails sticking out and disrupt the hydrogen bonding. This allows water to spread and wet the surface.

Figure .: :he sur ace tension o $ater causes it to orm droplets on clean sur aces

Jou can see this if you pour a little tap water onto a very clean porcelain surface such as a plate ' it will tend to form droplets. !dd a little washing up li-uid %which contains surfactants& and the water will spread to cover the whole plate. The function of surfactants is to reduce the surface tension of water and allow the a-ueous solution on which H!K8 ( is based to wet the porcelain surface of the toilet bowl effectively. This allows product to spread over the surface rather than form droplets.

=ther ingredients ,2 o 2%
8FI', hydrogenated tallow ammonium chloride and tallowtrimonium chloride are cationic detergents. They are based on -uaternary ammonium compounds and have structures like the one in :igure A.

Cl+H N 3

Figure 3: A #uaternar' ammonium compound sur actant

The ionic head mi$es with water while the hydrocarbon tail is non'polar. (ationic surfactants can be used in acid solution. Anionic sur actants such as soaps like the one in :igure H cannot be used in acid solutions because the hydrogen ions in the solution would react with the negative ions and protonate them. This produces a non' ionic and therefore insoluble compound
O ONa+

Figure 6: An anionic sur actant

!uestion 11 a% Identi ' the unctional group o the anionic sur actant in Figure 6* "% Write an e#uation to sho$ the protonation o this group* Laureth'56, :igure >, is a non7ionic sur actant based on the group 3 %(H,(H,)&n'. t is relatively polar with a non'polar hydrocarbon tail.
OH O n

Figure 8: A pol'eth'lene etho&'late 5 a non7ionic detergent

/on'ionic surfactants can also be used in acid solutions. ! further function of the tallow ammonium chloride is that it acts as a thickening agent so that the product will cling to the sides of the toilet pan and remain effective through many flushes. Harpic also contains a blue colouring agent so that the user can see clearly where the product is and can make sure that the whole of the toilet rim is covered, a task that would be more difficult with a colourless li-uid. The acid in Harpic means that it is an effective germicide, killing <<.<7 of germs.

Further in ormation
Harpic is sold in the LM by Keckitt Cenckiser %www.reckittbenckiser.comGsiteGKMCKGTemplatesG)urCrands4urface(are.as p$Npageid;,A*&. There are other branded products which work in a similar way.

Ac)no$ledgements
The Koyal 4ociety of (hemistry wishes to thank (hris Oones and Pavid Mennedy of Keckitt Cenckiser for help in preparing this material.

!DE(:I=E( AE+ AE(WER(

!uestion 1 Write "alanced e#uations to sho$ ho$ a% sul ur "urns in o&'gen to orm sul ur dio&ide 4%s& + ),%g& 4),%g& "% reacts $ith urther o&'gen to orm sul ur trio&ide 4),%g& + Q ),%g& 4)*%g& c% ho$ sul ur trio&ide reacts $ith $ater in the atmosphere to orm sul uric acid 4)*%g& + H,)%l& H,4)9%a-& !uestion 2 (uggest t$o reasons $h' limescale tends to orm more around the hot tap than the cold tap in a "athroom sin)* The water evaporates due to the heat of the hot tap. The e-uilibrium moves to the left %by Le (hateliers principle& ie the direction in which it absorbs heat. !uestion H'drochloric acid is a solution o h'drogen chloride gas* a% Wor) out the volume ,at standard temperature and pressure% o h'drogen chloride dissolved in 1 dm- o Harpic* The volume of 5 mole of any gas at room temperature is appro$imately ,9 666 cm*. 4o the volume of dissolved gas in a solution of * mol dm'* H(l is appro$imately >, 666 cm*. "% Wor) out the mass o h'drogen chloride dissolved in 1 dmHarpic*

Br of H(l is 5 + *A.A ; *H.A g mol'5 so the mass of * mol H(l ; 56<.A g. !uestion . Calculate /HCl0 to produce a pH o 1 pH ; 'log56?H+@ 6 ; 'log56?H+@ ?H+@ ; inv log566 ?H+@ ; 5 mol dm'* (ompare this to the concentration of H(l in Harpic which is * times higher. nterestingly Harpic has a pH of '6.9=. !uestion 3 What is the s'stematic name o Bethanoic acid. ormic acid?

!uestion 6 Calculate the pH o a 1 mol dm7- solution o sul amic acid* The pKa of sulfamic acid is 6.<< pKa ; 3log56 Ka so Ka ; 56' 6.<< Ka ; 6.56 mol dm'* H)4),/H, R )4),/H,' + H+

Ka ;

[OSO 2NH 2 - (aq) ] eqm [H + (aq) ] eqm [HOSO 2NH 2 (aq) ] eqm

?)4),/H,'%a-&@e-m ; ?H+%a-&@e-m ?H)4),/H,%a-&@e-m; 5 ' ?H+%a-&@e-m S 5 %#e can safely make this assumption for a weak acid&

[H + (aq) ] 2 eqm 4o 6.56 ; 1

?H+%a-&@e-m ; T6.56 ; 6.*5H mol dm'* pH ; 3log56 ?H+%a-&@e-m ; 6.A !uestion 8

a% E&plain $h'2 $hen ormic acid dissociates2 the h'drogen atom "onded to an o&'gen is the one lost as a H9 ion rather than the one "onded to the car"on atom* )$ygen is significantly more electronegative than hydrogen %*.A as opposed to ,.5&. 4o the )'H bond is polarised )U' ' HU+ making loss of the hydrogen as H+ easy. (arbons electronegativity is similar to that of hydrogen %,.A to ,.5& so the ('H bond is relatively non'polar and there is little tendency for the H atom to ac-uire a positive charge. "%:he pKa o ormic acid is -*;2 $hat is the value o Ka? <ive the correct units pKa ; 3log56 Ka so Ka ; 5.H $ 56'* mol dm'* c% Write an e&pression or Ka o HC==H% [HCOO - (aq) ] eqm [H + (aq) ] eqm Ka ; [HCOOH (aq) ] eqm ormic acid ,represent the acid as

d% Calculate the pH o a 1 mol dm7- solution o ?H())' %a-&@e-m ; ?H+%a-&@e-m ?H())H%a-&@e-m; 5 ' ?H+%a-&@e-m S 5

ormic acid*

%#e can safely make this assumption for a weak acid& 4o 5.H $ 56'* ;

[H + (aq) ] 2 eqm 1

?H+%a-&@e-m ; T5.H $ 56'* ; 6.69 mol dm'* pH ; 3log56 ?H+%a-&@e-m ; 5.9

e% Compare 'our ans$er or the pH o ormic acid $ith that o 1 mol dm7- h'drochloric acid ,HCl%2 a strong acid* Hydrochloric acid dissociates completely in solution H(l%a-& H+%a-& + (l'%a-&

4o ?H+@e-m ; 5 mol dm'* pH ; 3log56 ?H+%a-&@e-m ; 6

!uestion ; A similar product to Harpic states on the pac) ?this uni#ue ormula sho$s 'ou $here it is $or)ing "' turning rom green to "lue and i@@ing on contact $ith limescaleA* E&plain the i@@ing and sggest ho$ the colour change ma' "e "rought a"out*

The fiEEing is carbon dio$ide produced by the reaction of hydrochloric acid and calcium carbonate in the limescale. The colour change could be brought about by adding a suitable acid base indicator that changes colour as the acid is used up. !uestion B Calculate ho$ much chlorine could "e produced rom a t'pical dose o Harpic o 31 cm- assuming that there $as e&cess "leach* H(l)%a-& + H(l%a-& (l,%g& + H,)%l& !ssume the e-uilibrium is forced completely to the right. 5 mol H(l will produce 5 mol chlorine n a A6 cm* dose of Harpic of concentration 5 mol dm'* Boles H(l ;
C xV 1 x 50 ; ; A $ 56', mol 1000 1000

4o A $ 56', mol (l, will be produced !t room temperature 5 mole of any gas has an appro$imate volume of ,9 dm* %,9 666 cm*& 4o volume (l, ; ,9 666 $ A $ 56', cm* ; 5,66 cm* Mr (l, ; >5, so this is e-uivalent to a mass of chlorine of >5 $ A $ 56', g ; *.AA g or *AA6 mg. !uestion 11 a% Identi ' the unctional group o the anionic sur actant in Figure 6* (arbo$ylic acid %the sodium salt of a carbo$ylic acid& ())'. "% Write an e#uation to sho$ the protonation o this group* K())' + H+ V K())H