Copper (II) chloride: Difference between revisions

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{{Compound|aka=cupric chloride|chemf=CuCl2|group=salts
{{Compound|aka=cupric chloride|chemf=CuCl2|group=salts
|mm=134.45|density=3.386|mp=498|bp=993 (decomp)|sol_aq=757|sol_et=530|sol_met=680|sol_ac=30|sol_det=1.1
|mm=134.45(anh)<br/>170.48(dihydrate)|density=3.386|mp=498|bp=993 (decomp)|sol_aq=757|sol_et=530|sol_met=680|sol_ac=30|sol_det=1.1
|stp_p=solid|stp_q=yellow-brown
|stp_p=solid|stp_q=yellow-brown
|nfpa_h=2|nfpa_r=1
|nfpa_h=2|nfpa_r=1
Line 7: Line 7:
===Other===  
===Other===  
* Catalyst for the production of [[sulfuric acid]]
* Catalyst for the production of [[sulfuric acid]]
* Metal Etchant
* Metal etchant
==Natural occurrence==  
 
==Natural occurrence==
* '''Does''' occur naturally as the very rare minerals tolbachite and eriochalcite
 
==Hazards==
==Hazards==
Soluble copper compounds are toxic to mammals and can be deadly to fish.
Soluble copper compounds are toxic to mammals and can be deadly to fish.
==Production==  
==Production==  
===Synthesis===
===Synthesis===
The main routes are divided by the source of the chloride ion.
The main routes are divided by the source and valence of the copper, and the source of the chloride ion.


{|class="wikitable dtab"
{|class="wikitable" style='width: 30%; float: right; margin-left:1.5em;'
|+Production of copper chloride
|+Production of copper chloride
!colspan=2 rowspan=2|&nbsp;
!rowspan=2|&nbsp;
!colspan=3|Source of chlorine ion
!colspan=3|Source of chlorine ion
|-
|-
!aerated [[hydrochloric acid]]
![[hydrochloric acid]] (aerated)
!warmed [[ammonium chloride]]
![[ammonium chloride]]
![[chlorine|chlorine gas]]
![[chlorine|chlorine gas]]
|-
|-
!rowspan=100|Source of copper
!colspan=4 style='text-align:center;'|Copper (0)
![[copper|copper metal]]||{{gcheck}}||?||{{gcheck}}
|-
![[copper{{!}}copper metal]]||{{gcheck}}||?||{{gcheck}}
|-
|-
![[copper (I) chloride]]||{{gcheck}||?||?
!colspan=4|Copper (I)
|-
|-
![[Malachite]]||{{gcheck}}||?||?
![[copper (I) chloride]]||{{gcheck}}||?||?
|-
|-
![[Azurite]]||{{gcheck}}||?||?
!'''Chalcocite'''<br/>'''copper (I) sulfide'''|||?||?||?
|-
|-
!'''Covellite'''||?||?||?
!'''Cuprite'''<br/>'''copper (I) oxide'''||?||?||?
|-
|-
!'''Chalcocite'''||?||?||?
!colspan=4 style='text-align:center;'|Copper (II)
|-
|-
![[Copper (II) oxide]]||{{gcheck}}||?||?
![[Copper (II) oxide]]||{{gcheck}}||{{gcheck}}||?
|-
|-
![[Copper (II) sulfide]], [[chalcocite]]||{{gcheck}}||?||?
!'''copper (II) sulfide'''||{{gcheck}}||{{gcheck}}||?
|-
![[Malachite]]||{{gcheck}}||{{gcheck}}||?
|-
![[Azurite]]||{{gcheck}}||{{gcheck}}||?
|-
![[Copper (II) acetate]]||{{gcheck}}||?||'''no'''
|-
![[Copper (II) hydroxide]]||?||?||?
|}
|}
====via chlorine====
<div style='margin-left: 2em;'>
=====metallic copper=====
At or above red heat (~500&deg;C), [[copper]] reacts directly with gaseous [[chlorine]], giving molten {{#Chem:CuCl2}}. The reaction is sufficiently exothermic that the reaction will continue once started.
</div>


====via hydrochloric acid====
====via hydrochloric acid====
Line 53: Line 60:
*: {{#Chem: 4Cu + 4HCl + O2 = 4CuCl + 2H2O // from copper(0) to copper (I)}}
*: {{#Chem: 4Cu + 4HCl + O2 = 4CuCl + 2H2O // from copper(0) to copper (I)}}
*: {{#Chem: 4CuCl + 4HCl + O2 = 4CuCl2 + 2H2O // from copper(I) to copper (II)}}
*: {{#Chem: 4CuCl + 4HCl + O2 = 4CuCl2 + 2H2O // from copper(I) to copper (II)}}
=====copper (II) minerals=====
* Combine [[malachite]] and [[hydrochloric acid]]
*: {{#Chem: Cu2(OH)2CO3 + 4 HCl = 2 CuCl2 + 3 H2O + CO2}}
=====copper (I) chloride=====
=====copper (I) chloride=====
* Bubble air through [[copper (I) chloride]] in [[hydrochloric acid]]. This will ''not'' work without the air, and even then it takes ''days''. <ref>{{cite patent|2586579|title=Method of production of cuprous oxide and copper chlorides}}</ref>
* Bubble air through [[copper (I) chloride]] in [[hydrochloric acid]]. This will ''not'' work without the air, and even then it takes ''days''. <ref>{{cite patent|2586579|title=Method of production of cuprous oxide and copper chlorides}}</ref>
*: {{#Chem: 4CuCl + 4HCl + O2 = 4CuCl2 + 2H2O // from (I) to (II)}}
*: {{#Chem: 4CuCl + 4HCl + O2 = 4CuCl2 + 2H2O // from (I) to (II)}}
=====copper (II) minerals=====
* Combine [[malachite]] and [[hydrochloric acid]]
*: {{#Chem: Cu2CO3(OH)2 + 4 HCl = 2 CuCl2 + 3 H2O + CO2}}
* Combine [[azurite]] and [[hydrochloric acid]]
*: {{#Chem: Cu3(CO3)2(OH)2 + 6 HCl = 3 CuCl2 + 4 H2O + 2 CO2}}
</div>
</div>
====via ammonium chloride====
====via ammonium chloride====
<div style='margin-left: 2em;'>
=====copper hydroxide=====
# Combine [[ammonium chloride]] and damp [[copper (II) hydroxide]]
# Mix thoroughly, allowing the compounds to react
# Heat above 40&deg;C, driving off the ammonium hydroxide
#:'''NB''' keep temperature below 200&deg;C to prevent decomposing the '''copper hydroxide'''
#:        keep temperature below 350&deg;C to prevent decomposing the '''ammonium chloride'''
#:        Both ammonium hydroxide and copper chloride are thermally stable.
=====copper carbonate / malachite / azurite=====
=====copper carbonate / malachite / azurite=====
These reactions work in the presence of excess [[ammonium chloride]]
: {{#Chem:4 NH4Cl + Cu2CO3(OH)2 = 2 CuCl2 + 3 H2O + 4 NH3 + CO2 //  2x excess of -chloride }}
: {{#Chem:6 NH4Cl + Cu3(CO3)2(OH)2 = 3 CuCl2 + 4 H2O + 6 NH3 + 2 CO2 // '''UNTESTED'''}}
=====copper (II) oxide / sulfide=====
=====copper (II) oxide / sulfide=====
Hydrochlorination of the copper(II) compounds begins at 190&deg;C to form ammonium chlorocuprates, {{#Chem:(NH4)2CuCl4}} in with [[copper (II) oxide]] and {{#Chem:NH4CuCl3}} with copper (II) sulfide, which at the temperature higher than 300&deg;C decompose affording [[copper (II) chloride|{{#Chem:CuCl2}}]]<ref>{{cite pub
...hydrochlorination of the copper(II) compounds begins at 190&deg;C to form ammonium chlorocuprates, {{#Chem:(NH4)2CuCl4}} in with [[copper (II) oxide]] and {{#Chem:NH4CuCl3}} with copper (II) sulfide, which at the temperature higher than 300&deg;C decompose affording [[copper (II) chloride|{{#Chem:CuCl2}}]]<ref>{{cite pub
|publication=Russian Journal of General Chemistry
|publication=Russian Journal of General Chemistry
|year=2011
|year=2011
Line 80: Line 103:
|doi=10.1134/S107036321107005X
|doi=10.1134/S107036321107005X
}}</ref>
}}</ref>
# Combine (dry) [[ammonium chloride]] and [[copper (II) oxide]] in a flask
   
# Direct gasses from flask through {{#Chem: CaO}} dryer, then a suckback trap, and thence to a water bubbler.
'''Compound  I.'''  A  mixture  of  copper oxide, 6.67  g, and ammonium  chloride,  17.61  g,  was  calcined  at  a temperature of 320&deg;C for 12 h.
# Heat to 190&deg;C
'''Compound  II.'''  Prepared  similarly  from  5.46  g  of  copper sulfide and 18.04 g of ammonium chloride at a temperature of 320&deg;C for 12 h
#: {{#Chem: 4 NH4Cl(s) + CuO(s) { = 190&deg;C } (NH4)2CuCl4(s) + NH4OH(g) + NH3(g) // gasses condense or are absorbed by water }}
# Combine 1ubm [[copper (II) oxide]] and 2.6ubm dry [[ammonium chloride]]
# remove dryer
# Heat to 320&deg;C for 12h
# Heat to 300&deg;C  
#: {{#Chem: 2 NH4Cl + CuO { = 320&deg;C} CuCl2 + H2O + 2 NH3 }}
#: {{#Chem: (NH4)2CuCl4 { = 300&deg;C } CuCl2(s) + 2 NH4Cl(g) // may condense in trap or be absorbed in bubbler}}
#: {{#Chem: (NH4)2CuCl4 { = 338&deg;C } CuCl2(s) + 2 NH3(g) + 2 HCl(g) // may recombine to 2 NH4Cl in trap, or be absorbed in bubbler.}}
# Remove bubbler
# Cool to RT with dryer in place.
# Cool to RT with dryer in place.
</div>
</div>
====via chlorine====
<div style='margin-left: 2em;'>
=====metallic copper=====
At or above red heat (~500&deg;C), [[copper]] reacts directly with gaseous [[chlorine]], giving molten {{#Chem:CuCl2}}. The reaction is sufficiently exothermic that the reaction will continue once started.
</div>
====via calcium chloride====
Metathesis reaction between [[copper (II) sulfate]] with [[calcium chloride]] or '''barium chloride''', producing copper chloride in solution and calcium sulfate as a precipitate. Obviously this is only useful after the production of both materials, so there's a bootstrapping problem.
:{{#Chem: CuSO4 + CaCl2 = CuCl2 + CaSO4}}
:{{#Chem: CuSO4 + BaCl2 = CuCl2 + BaSO4}}


==Purification==
==Purification==
Recrystallize from hot dilute aqueous HCl by cooling in a [[calcium chloride]]-ice bath
Recrystallize from hot dilute aqueous HCl by cooling in a [[calcium chloride]]-ice bath
==Testing==
==Testing==
* Visual: Dark blue-green crystals
* Visual: Yellow-brown (anhydrous) dark green (excess chloride) or bright blue (partially hydrated) crystals
* Reacts vigorously with [[aluminum]]
* Reacts vigorously with [[aluminum]]
*: {{#Chem: 3CuCl2 + 2Al = 3Cu + 2AlCl3}}
*: {{#Chem: 3CuCl2 + 2Al = 3Cu + 2AlCl3}}

Revision as of 07:36, 10 May 2020

 
Copper (II) chloride
aka cupric chloride
Chemical formula CuCl2
OTP appearance yellow-brown solid 
Molar Mass(g/mol) 134.45(anh)
170.48(dihydrate) 
Density(g/cc) 3.386 
Melting Point(°C) 498 
Boiling Point(°C) 993 (decomp) 
Solubility in water(g/L) 757 
Solubility in ethanol(g/L) 530 
Solubility in methanol(g/L) 680 
Solubility in ether(g/L) 1.1 
Solubility in acetone(g/L) 30
NFPA 704
NFPA704.png
0
2
1
 

 

Thermal Decomposition
copper (II) chloride
993°C
CuCl,Cl2

Uses

Other

Natural occurrence

  • Does occur naturally as the very rare minerals tolbachite and eriochalcite

Hazards

Soluble copper compounds are toxic to mammals and can be deadly to fish.

Production

Synthesis

The main routes are divided by the source and valence of the copper, and the source of the chloride ion.

Production of copper chloride
  Source of chlorine ion
hydrochloric acid (aerated) ammonium chloride chlorine gas
Copper (0)
copper metal ?
Copper (I)
copper (I) chloride ? ?
Chalcocite
copper (I) sulfide
? ? ?
Cuprite
copper (I) oxide
? ? ?
Copper (II)
Copper (II) oxide ?
copper (II) sulfide ?
Malachite ?
Azurite ?
Copper (II) acetate ? no
Copper (II) hydroxide ? ? ?

via hydrochloric acid

metallic copper
  • Bubble air through copper metal immersed in hydrochloric acid. This will not work without the air, and even then it takes days. This may go in two separate steps, first to copper (I) chloride, and thence to copper(II) chloride, shown separately below.
    4 Cu + 4 HCl + O2 4 CuCl + 2 H2O // from copper(0) to copper (I)
    4 CuCl + 4 HCl + O2 4 CuCl2 + 2 H2O // from copper(I) to copper (II)
copper (I) chloride
  • Bubble air through copper (I) chloride in hydrochloric acid. This will not work without the air, and even then it takes days. [1]
    4 CuCl + 4 HCl + O2 4 CuCl2 + 2 H2O // from (I) to (II)
copper (II) minerals

via ammonium chloride

copper hydroxide
  1. Combine ammonium chloride and damp copper (II) hydroxide
  2. Mix thoroughly, allowing the compounds to react
  3. Heat above 40°C, driving off the ammonium hydroxide
    NB keep temperature below 200°C to prevent decomposing the copper hydroxide
    keep temperature below 350°C to prevent decomposing the ammonium chloride
    Both ammonium hydroxide and copper chloride are thermally stable.
copper carbonate / malachite / azurite

These reactions work in the presence of excess ammonium chloride

4 NH4Cl + Cu2CO3(OH)2 2 CuCl2 + 3 H2O + 4 NH3 + CO2 // 2x excess of -chloride
6 NH4Cl + Cu3(CO3)2(OH)2 3 CuCl2 + 4 H2O + 6 NH3 + 2 CO2 // UNTESTED
copper (II) oxide / sulfide
...hydrochlorination of the copper(II) compounds begins at 190°C to form ammonium chlorocuprates, (NH4)2CuCl4 in with copper (II) oxide and NH4CuCl3 with copper (II) sulfide, which at the temperature higher than 300°C decompose affording CuCl2[2]

Compound  I.  A  mixture  of  copper  oxide,  6.67  g,  and  ammonium  chloride,  17.61  g,  was  calcined  at  a  temperature of 320°C for 12 h.
Compound  II.  Prepared  similarly  from  5.46  g  of  copper sulfide and 18.04 g of ammonium chloride at a temperature of 320°C for 12 h
  1. Combine 1ubm copper (II) oxide and 2.6ubm dry ammonium chloride
  2. Heat to 320°C for 12h
    2 NH4Cl + CuO
    {
    320°C}
    CuCl2 + H2O + 2 NH3
  3. Cool to RT with dryer in place.

via chlorine

metallic copper

At or above red heat (~500°C), copper reacts directly with gaseous chlorine, giving molten CuCl2. The reaction is sufficiently exothermic that the reaction will continue once started.

via calcium chloride

Metathesis reaction between copper (II) sulfate with calcium chloride or barium chloride, producing copper chloride in solution and calcium sulfate as a precipitate. Obviously this is only useful after the production of both materials, so there's a bootstrapping problem.

CuSO4 + CaCl2 CuCl2 + CaSO4
CuSO4 + BaCl2 CuCl2 + BaSO4

Purification

Recrystallize from hot dilute aqueous HCl by cooling in a calcium chloride-ice bath

Testing

  • Visual: Yellow-brown (anhydrous) dark green (excess chloride) or bright blue (partially hydrated) crystals
  • Reacts vigorously with aluminum
    3 CuCl2 + 2 Al 3 Cu + 2 AlCl3

Storage

  • Do not store with excess copper. This can result in decomposition to copper (I) chloride:
    Cu + CuCl2 2 CuCl
  • Do not store in acidic conditions.

Disposal

See Also

References

  1. US patent 2586579 "Method of production of cuprous oxide and copper chlorides"
    Link courtesy Google
  2. Borisov, V.A.; D’yachenko, A.N; Kraidenko, R.I. (2011) "Reaction of Ammonium Chloride with the Copper(II) Sulfide and Oxide, and Identification of the Reaction Products"
    Russian Journal of General Chemistry 81(7); pp1430–1433. 
    DOI:10.1134/S107036321107005X
    link courtesy researchgate.