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
|decomp={{DecompRow|input=copper (II) chloride|temp=993|output={{#Chem:  CuCl, Cl2}}}}}}  
==Uses==  
==Uses==  
===Other===  
===Other===  
* Precursor for [[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 simplest is hydrochloric acid:
The main routes are divided by the source and valence of the copper, and the source of the chloride ion.
====via hydrochloric acid====
 
<div style='margin-left: 2em;'>
{|class="wikitable" style='width: 30%; float: right; margin-left:1.5em;'
=====metallic copper=====
|+Production of copper chloride
* 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.
*: {{#Chem: 4Cu + 4HCl + O2 = 4CuCl + 2H2O // from copper(0) to copper (I)}}
*: {{#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=====
* Bubble air through [[copper (I) chloride]] in [[hydrochloric acid]]. This will ''not'' work without the air, and even then it takes ''days''.
*: {{#Chem: 4CuCl + 4HCl + O2 = 4CuCl2 + 2H2O // from (I) to (II)}}
</div>
====via sodium chloride====
<div style='.td {text-align:right;} tr.X th{ background-color:red;}'>
{|class=dtab
|+Relative Solubilities
!rowspan=2|&nbsp;
!rowspan=2|&nbsp;
!colspan=2|water
!colspan=3|Source of chloride ion
!colspan=2|ethanol
|-
![[hydrochloric acid]] (aerated)
![[ammonium chloride]]
![[chlorine|chlorine gas]]
|-
|-
!g/L
!colspan=4 style='text-align:center;'|Copper (0)
!M
!g/L
!M
|-
|-
!copper&nbsp;chloride||757||5.63||style='background-color:#c0c0c0;color:#000'|530.00||style='background-color:#c0c0c0;color:#000'|3.94
![[copper{{!}}copper metal]]||{{gcheck}}||?||{{gcheck}}
|-
|-
!sodium&nbsp;chloride||359|||6.10|||0.65|||0.01
!colspan=4|Copper (I)
|-
|-
!copper acetate||65||0.36||71.40||0.39
![[copper (I) chloride]]||{{gcheck}}||?||?
|-
|-
!sodium acetate||1233||15.00||23.00||0.28
!'''Chalcocite'''<br/>'''copper (I) sulfide'''|||?||?||?
|-
|-
!copper sulfate||200||1.26||ins||0
!'''Cuprite'''<br/>'''copper (I) oxide'''||?||?||?
|-
|-
!sodium sulfate||139||1.02||ins||0
!colspan=4 style='text-align:center;'|Copper (II)
|-
![[Copper (II) oxide]]||{{gcheck}}||{{gcheck}}||?
|-
!'''copper (II) sulfide'''||{{gcheck}}||{{gcheck}}||?
|-
![[Malachite]]||{{gcheck}}||{{gcheck}}||?
|-
![[Azurite]]||{{gcheck}}||{{gcheck}}||?
|-
![[Copper (II) acetate]]||{{gcheck}}||?||?
|-
![[Copper (II) hydroxide]]||?||?||?
|}
|}
</div><div style='margin-left: 2em;'>
; 0.035M (100ml) scale
# Gather 6.7g of [[copper (II) acetate]] monohydrate
# Heat to 160&deg;C (325F) for 10 minutes to drive off the water
# Measure mass again: should be 6.33g
# Dissolve in 100ml dried ethanol (saturated limit, 0.35M)
# Transfer ethanol to separation funnel
# Prepare saturated saline solution (6M)
# Repeat
## Add 5.7ml of saturated saline solution to ethanol in sep funnel, shaking regularly
## Draw off aqueous layer and evaporate
##: NB: Should contain mostly sodium acetate, less sodium chloride.
# Until mostly sodium acetate remains
# Evap the ethanol layer, leaving mostly copper chloride
When using salt as a source of chlorine, choose an anion whose copper salt that is more soluble in water than ethanol, such as [[copper (II) acetate]] or [[copper sulfate]], and preferably an anion for which the sodium salt also prefers water. Mix them in a water/ethanol solution, and allow the copper chloride to dominate the ethanol phase.


====via hydrochloric acid====
<div style='margin-left: 2em;'>
=====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.
*: {{#Chem: 4Cu + 4HCl + O2 = 4CuCl + 2H2O // from copper(0) to copper (I)}}
*: {{#Chem: 4CuCl + 4HCl + O2 = 4CuCl2 + 2H2O // 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''. <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)}}
=====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;'>
<div style='margin-left: 2em;'>
# Combine (dry)  [[ammonium chloride]] and [[copper (II) oxide]] in a flask
=====copper carbonate / malachite / azurite=====
# Direct gasses from flask through {{#Chem: CaO}} dryer, then a suckback trap, and thence to a water bubbler.
These reactions work in the presence of excess [[ammonium chloride]]
# Heat to 190&deg;C
: {{#Chem:4 NH4Cl + Cu2CO3(OH)2 = 2 CuCl2 + 3 H2O + 4 NH3 + CO2 // 2x excess of -chloride }}
: {{#Chem: 4 NH4Cl(s) + CuO*(s) { = 190&deg;C } (NH4)2CuCl4(s) + NH4OH(g) + NH3(g) // gasses condense or are absorbed by water }}
: {{#Chem:6 NH4Cl + Cu3(CO3)2(OH)2 = 3 CuCl2 + 4 H2O + 6 NH3 + 2 CO2 // '''UNTESTED'''}}
# swap suckback trap and dryer
# Heat to 300&deg;C
: {{#Chem: (NH4)2CuCl4 { = 300&deg;C } CuCl2(s) + 2 NH4Cl(g) // may condense in trap or react in dryer
: {{#Chem: (NH4)2CuCl4 { = 338&deg;C } CuCl2(s)  + 2 NH3(g) + 2 HCl(g) // recombines to 2 NH4Cl in suckback trap, HCl reacts with dryer, NH3 absorbed in bubbler.
# Remove bubbler
# Cool to RT with dryer in place.


  ...hydrochlorination of the copper(II) compounds begins at 190&deg;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&deg;C decompose affording [[copper (II) chloride|{{#Chem:CuCl2}}]]<ref>{{cite pub
=====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
|publication=Russian Journal of General Chemistry
|publication=Russian Journal of General Chemistry
|year=2011
|year=2011
Line 98: Line 94:
|url=https://www.researchgate.net/publication/251412801_Reaction_of_ammonium_chloride_with_the_copperII_sulfide_and_oxide_and_identification_of_the_reaction_products
|url=https://www.researchgate.net/publication/251412801_Reaction_of_ammonium_chloride_with_the_copperII_sulfide_and_oxide_and_identification_of_the_reaction_products
|courtesy=researchgate
|courtesy=researchgate
|doi=10.1134/S107036321107005X
}}</ref>
}}</ref>
'''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.
'''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
# Combine 1ubm [[copper (II) oxide]] and 2.6ubm dry [[ammonium chloride]]
# Heat to 320&deg;C for 12h
#: {{#Chem: 2 NH4Cl + CuO { = 320&deg;C}  CuCl2 + H2O + 2 NH3  }}
# Cool to RT with dryer in place.
</div>
</div>


==Testing==
====via chlorine====
* There is an exothermic reaction with aluminum and aluminum oxide
<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====
=====copper (II) sulfate=====
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}}
=====copper (II) acetate=====
#Combine [[calcium chloride]] with [[copper (II) acetate|copper acetate]] in [[ethanol]]
#: Filter solution. Residue is [[calcium acetate]]
# Evaporate filtrate. Residue is [[copper (II) chloride|copper chloride]]


==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==
* Visual: Yellow-brown (anhydrous) dark green (excess chloride) or bright blue (partially hydrated) crystals
* Reacts vigorously with [[aluminum]]
*: {{#Chem: 3CuCl2 + 2Al = 3Cu + 2AlCl3}}


==Storage==
==Storage==
Line 117: Line 137:


==See Also==
==See Also==
* {{cite patent|2587579|title=Method of production of cuprous oxide and copper chlorides}}
* {{cite pub
|title=Reaction of ammonium chloride with the copper(II) sulfide and oxide, and identification of the reaction products
|year=2011
|publication=Russian Journal of General Chemistry
|volume=81
|issue=7
|pages=1430-1433
|doi=10.1134/S107036321107005X
|url=https://www.researchgate.net/publication/251412801_Reaction_of_ammonium_chloride_with_the_copperII_sulfide_and_oxide_and_identification_of_the_reaction_products
|first1=V. A.
|last1=Borisov
|first2=A. N.
|last2=D’yachenko
|first3=R. I.
|last3=Kraidenko
}}</ref>


==References==  
==References==  
<references/>
<references/>

Latest revision as of 01:05, 2 November 2023

 
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 chloride 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 ✔ ? ?
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 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

copper (II) sulfate

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
copper (II) acetate
  1. Combine calcium chloride with copper acetate in ethanol
    Filter solution. Residue is calcium acetate
  2. Evaporate filtrate. Residue is copper chloride

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.
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