HSC Chemistry 6.

0
Kai Anttila August 10, 2006 06120-ORC-T

18 - 1

18. ! " !H - Sam!les EpH module: #n!ut $ile %&r !H '&(ule

Eh - pH - Diagram 4.0 ' = Diagram type 2 Cu 1.0000, 1.0000 S 1.0000, 1.0000 2 25.000, 75.000 N -56.6781, -54.7567 1.0000, 1.0000 0 -2, 2, 0, 14 Cu , 0.0000, CuH , 67.7 1 , Cu! , - 0.6627, Cu2! , - 5. 446, Cu!#CuS!4 , -18". 5 , Cu$!H%2 , -85.8077, CuS , -12.7800, Cu2S , -20.6662, CuS!4 , -158.2417, Cu2S!4 , -156.42"4, CuS!4# H2! , - 4.5808, CuS!4#5H2! , -44".26 5, H2S!4 , -164.8848, H2S!4# H2! , - 45.1000, H2S!4#4H2! , -402."12 , S , 0.0000, S$&% , 0.01"0, S! $'% , -8".4025, S! $(% , -8".7786, Cu$)2a% , 15.6 00, Cu$)a% , 11."450, Cu$!H%2$a% , -5".55"6, CuS!4$a% , -162. 104, Cu2S! $a% , -"2.224 , H2S$a% , -6.5160, HS$-a% , 2."11 , H2S! $a% , -128.552", H2S!4$a% , -177."474, HS! $-a% , -126.1208, HS! $-2a% , -121. 4 0, HS!4$-a% , -180.6580, HS!4$-2a% , -175.2501, HS!5$-a% , -152. 5 2, S$-2a% , 20.5471, S2$-2a% , 1".0406, S $-2a% , 17.6446, S!2$a% , -71.8 54, S! $a% , -125.6 15, S! $-2a% , -116.2"71, S!4$-2a% , -177."474, S2! $-2a% , -12 ."775, S2!4$-2a% , -14 .5482, S2!5$-2a% , -188.026 , S2!6$-2a% , -2 1.6077, S2!8$-2a% , -266.4866, S !6$-2a% , -244.8178, ' ' ' ' Heading Number of Elements Name of a Element Molality and pressure of this Element

' Number of temperatures ' Values of Temperatures in C ' Show stability areas of ions ( !N" ' # $alues of H%& for all temperatures ' 'iele(tri( Constant ' )on strenght ' *imits of the diagram 0.0000 ) *ame &% a s!e+ies an( , -alues %&r all tem!eratures 68.0470 -2".55 - 4.42"4 -18 ."282 -82.44 7 -12.7"52 -20.8844 -15 .8574 -152.5214 - 2 .1528 -4 .1"54 -15"." "7 - 4.0"07 - 8"."61 0.0000 0.0068 -86.228 -86.70"4 15.7 17 11.0"01 -5 .626 -155.5767 -87.8581 -6.1670 4.2276 -125.6145 -171.0575 -122.2 17 -116.7 42 -175.408 -16". 171 -147.0"25 22.64 8 21.08"5 1".6504 -71.1"81 -121.1608 -110.0146 -171.1 8 -118.6055 -1 7.2786 -180.68"6 -22 . 17" -257. 452 -2 6.2"48

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 2

!H Case 1: Metal Corrosion in Fe-H2O-system

Eh-pH-diagrams may be used to estimate corrosion behavior of different metals in aqueous solutions !he most common corrosion phenomenon is rust formation on the iron surfaces !he corrosion rates and types depend on the chemical conditions in the aqueous solution !he Eh-pH-diagram of an Fe-H2O-system may easily be created as described in Chapter "# !he chemical system specification is sho$n in Fig " and the calculated diagram in Fig 2 !he stability areas may be divided into three groups"%:
1.

C&rr&si&n area: Formation of ions means that metal dissolves into an aqueous solution For e&ample' Fe()%a*' Fe()2a*' FeO2(-a* and HFeO2(-a*-ions in an Fe-H2Osystem .assi-e area: Formation of o&ides or some other condensed compounds may create tight film (impermeable* on the metal surface $hich passivates the surface' good e&amples are +l2O% on aluminium or !iO2 on titanium surfaces ,f the o&ide layer is not tight enough (porous* to prevent o&ygen diffusion into the metal surface' corrosion may continue !his is the case $ith the most of the iron o&ides but they may also cause passivation in favourable conditions #mmunity area: +ll metals are stable if the electrochemical potential is lo$ enough Most noble metals are stable even at -ero potential' but at least ./ 0 volts are needed at the cathode for iron to precipitate' see Fig 2

2.

/.

!he stability areas of $ater are sho$n by dotted blue lines in Eh-pH-diagrams' see Fig 2' the colors can not be seen in this 123 copy 4sually it is difficult to e&ceed these limits due to the formation of o&ygen at the upper limit and hydrogen at the lo$er limit ,n some solutions these limits may be e&ceeded due the necessary overpotential of hydrogen and o&ygen formation On the basis of Fig 2 it seems that hydrogen formation occurs on cathode before the metallic iron comes stable !he Eh-pH-diagrams may be used in several $ays' for e&ample' to find pH' potential and temperature regions $hich prevent corrosion to find out $hich compounds are the corrosion reaction products to find immune materials $hich can be used as protective coating to find out a metal $hich may corrode instead of the constructive material For e&ample' the -inc layer on a steel surface

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - /

$ig. 1. 5pecification of Fe-H2O-system for EpH-diagram at 26 7C

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 0

$ig. 2. Eh-pH 8iagram of Fe-H2O-system at 26 7C Molality of Fe is "/-0 M

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 1

!H Case 22

Corrosion ,nhibitors in Fe-Cr-H2O-system

5ome elements or compounds may prevent corrosion even at very lo$ content in the chemical system !hese substances are called corrosion inhibitors and they can be divided into anodic and cathodic inhibitors !he anodic inhibitors primarily prevent the anodic reaction and passivate metals in this $ay' the latter ones suppress the corrosion rate by preventing the cathodic reaction or by reducing the cathodic area "% Chromate and dichromate ions are $ell 9no$n anodic corrosion inhibitors 5mall amounts of chromates $ill create a tight comple& o&ide film on the steel surface $hich prevents corrosion !he o&ide film is mainly formed of magnetite (Fe%O:*' hematite (Fe2O%* and chromic o&ide (Cr2O%* !he inhibitor behavior of chromates may be illustrated $ith Eh-pH-diagrams !he Fe-CrH2O-system specifications are sho$n in Fig % !he calculation results for Fe-H 2O and FeCr-H2O-systems are sho$n in Figs : and 6 +s sho$n in the diagrams' a large area in the corrosion region of iron Fe()2a*' Fig :' is covered by the Cr 2O% and Cr 2FeO: stability areas and thus protected from corrosion' Fig 6 ,t is easy to create Eh-pH-diagrams $ith the EpH module Ho$ever' you should remember that this type diagram greatly simplifies the real situation !hey do not ta9e into account' for e&ample' the 9inetic aspects or non-ideality of real solutions 5mall errors in the basic thermochemical data may also have a visible effect on the location of the stability areas ,n any case' these diagrams give valuable qualitative information of the chemical reactions in aqueous systems in brief and illustrative form

$ig. /. 5pecification of Fe-H2O-system for EpH-diagram at "// and %// 7C

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 6

$ig. 0. Fe-H2O-system at "// 7C Molality: Fe "/-2 M' pressure " bar

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 3

$ig. 1. Fe-Cr-H2O-system at "// 7C Molalities: Fe and Cr "/-2 M' pressure " bar

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 8

!H Case /2

5election of ;eaching Conditions

!he first step in a hydrometallurgical process is usually leaching or dissolution of the ra$ materials in aqueous solution !he aim is to select the most suitable leaching conditions so that the valuable metals dissolve and the rest remain in the solid residue !he leaching conditions may easily be estimated $ith Eh-pH-diagrams ,n favorable leaching conditions the valuable metals must prevail in solution as aqueous species and the others in solid state <oasted -inc calcine is the most common ra$ material for the hydrometallurgical -inc process ,t contains mainly -inc o&ide +n e&ample of Eh-pH-diagrams application in -inc o&ide leaching is sho$n in Fig #' see Fig 0 for chemical system specifications ,t can be seen from the diagram that acid or caustic conditions are needed to dissolve the =nO into solution"> ,n acid conditions the pH of the solution must be lo$ered belo$ a value of 6 6 ,n practical processes the pH must be even lo$er because the relative amount of -inc in the solution increases if the pH is ad?usted farther from the equilibrium line bet$een the =nO and =n()2a* areas !he dissolution of the =nO consumes hydrogen ions as can be seen from reaction ("* !herefore acid must continuously be added to the solution in order to maintain favorable leaching conditions 4nO ) 2 H()a* @ =n()2a* ) H2O A"B ,n caustic conditions -inc may be obtained in solution by the formation of the anion comple& =nO2(-2a* !he leaching reaction may be described by equation (2* 4nO ) H2O @ =nO2(-2a* ) 2H()a* A2B !he leaching conditions change' for e&ample' if sulfur is included in the chemical system !he effect of sulfur can be seen in Fig "/ Much smaller pH values are need to dissolve =n5 $hich has $ide stability area !his $ill lead to the formation of hydrogen sulfide gas and ions according to reaction (%* 4nS ) 2H()a* @ =n()2a* ) H25(g* A%B ,n o&idi-ing conditions a number of different aqueous species may result from the leaching reactions such as (:*' (6* and (0*' see Fig 0 ,n these reactions it is important to note that the consumption of reagents as $ell as generation of reaction products continuously change the solution conditions !hese conditions must be regulated by feeding more acid andCor removing reaction products in order to the maintain optimum conditions 4nS @ =n()2a* ) 5 ) 2e4nS ) :H2O @ =n()2a* ) H5O:(-a* ) #H()a* ) De4nS ) :H2O @ =n()2a* ) 5O:(-2a* ) DH()a* ) DeA:B A6B A0B

!he H5C dat a b a s e cont ains a lot of speci e s $hich ma y have a long forma tion time Nor mally it is wise to select only such specie s which are identified in real solutions for che mi c al syst e m specifications + syst e m specification $ith only com mo n speci e s include d is sho$n in Fig D and anot h e r one $ith all the specie s in Fig > !he selec t e d specie s ma y have a visible effect on the diagr a m s as can be see n by comp a ri ng Figs "/ and "2 as $ell as Figs "" and "% ,n some cas e s ' diagr a m s $ith all the specie s selec t e d into the calculation syst e m ma y give also valua bl e infor ma tion' Figs "2 and "%

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 5

$ig. 6. =n-H2O-system specifications

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 10

$ig. 3. =n-H2O-system at 26 7C 8iagram is based on specifications in Fig 0

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 11

$ig. 8. =n-5-H2O-system specifications' only identified species included

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 12

$ig. 5. =n-5-H2O-system specifications' all species included

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 1/

$ig. 10. =n-5-H2O-system at 26 7C based on specifications in Fig D

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 10

$ig. 11. 5-=n-H2O-system at 26 7C based on specifications in Fig D

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 11

$ig. 12. =n-5-H2O-system at 26 7C based on specifications in Fig >

HSC Chemistry 6.0

Kai Anttila August 10, 2006 06120-ORC-T

18 - 16

$ig. 1/. 5-=n-H2O-system at 26 7C based on specifications in Fig >