Uploaded May 2017 | Updated September 2026, 1 week ago
If Thiocyanate is added to a Bismuth(III) solution the color will change to yellow upon the formation of [Bi(SCN)6](3-).
If Thiocyanate is added to a Bismuth(III) solution the color will change to yellow upon the formation of [Bi(SCN)6](3-).

![Mercury Chemistry: Mercury(II)chromate
Much like the brown Mercury(I)chromate, we prepared before using HgCl2 instead of Hg2Cl2 a corresponding Hg[CrO4] can be prepared as well. After heating, you can quickly see the bright red color of Hg[CrO4]. Mercury Chemistry: Mercury(II)chromate](https://i.ytimg.com/vi/toITTSeY9Og/mqdefault.jpg)
![Chromium Chemistry: Burning (NH4)2[Cr2O7] (no volcano)
You are probably familiar with the famous Ammonium Dichromate volcano. If you light some (NH4)2[Cr2O7] it will form Cr2O3 while creating burning sparks that form a sort of volcano. We tried to do that but our Dichromate is quite wet, unfortunately. So we tried a different idea and heated it directly with the burner. The temperature is high enough to vaporize the water and burn the Dichromate, creating much more sparks than usually.
What is happening is that the system contains two parts, in Ammonia the Nitrogen is reduced. If it is oxidized a stable N-N triple bond forms. On the other hand, the Dichromate contains a highly oxidized Chromium(VI). The stable form is Cr(III) so in exchange Cr(VI) is reduced and N(-III) oxidized.
This is also the reason why we didnt dry our Dichromate for the volcano. Many of these combinations of Ammonium and strong oxidizers (e.g. Ammonium Nitrate) tend to combust when heated. The dry compound starts to decompose around the boiling point of water. Although Ammonium Dichromate is usually not that reactive. Chromium Chemistry: Burning (NH4)2[Cr2O7] (no volcano)](https://i.ytimg.com/vi/uCwS1bTaX-8/mqdefault.jpg)
 an NO (+*-) as Ligand
This is a very famous test for Nitrate-Ions:
In this case we added some Iron nails for one day to 38% H2SO4 and then added some of the clear solution to a KNO3 solution. If conc. H2SO4 is very carefully added a brown-purple ring forms.
The ring has the composition [Fe(H2O5)NO](2+).
For many years people believed that Iron has the Oxidation state +I in this compound since NO is actually a Nitrosyl NO(+). Other suggestions say its Fe(II) or Fe(III).
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Just thinking about this is sounds strange for this to be Fe(I). Fe(II) is really hard to store as solution since it easily oxidizes to Fe(III). Thus it should become an Fe(III) really easy and not an Fe(I) (where no real compounds exist, some exceptions of course). On the other hand Nitrate is reduced to NO so something clearly has to be oxidized for this to happen which is Fe(II) becoming Fe(III).
We can also look this up in the redox series:
NO3(-) + 4H3O(+) + 3e(-) to NO + 6H2O (U = 0,96 V)
Fe(II) to Fe(III) + e(-) (U = 0,77 V).
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But can NO act in three different ways as a ligand ?
As you can see in this picture, neutral NO is already a radical
http://daten.didaktikchemie.uni-bayreuth.de/umat/stickstoffoxide/no_moschema.gif
So we could write it as NO* for a second. If another electron is added to form NO(-) we reach something that reminds us of Oxygen and if we take an electron away to make NO(+) we can get something which is isoelectronic to Carbonyl (CO). And Oxygen and Carbonyl are famous Ligands. This is why all three seem possible depending on the electronic situation making the Iron a (I), (II) or (III). It gets even harder as there are multiple ways how NO can coordinate to a metal center, but we wont further discuss this here.
Quite new calculations and research show that it is really an Fe(III) and an NO(-) present.
But there is more! If you followed our video series you might have seen videos where we used Nitroprusside. In Nitroprusside an NO(+) is present. If this compound is reduced even further you might expect NO* to form. Analyzing the products showed that for some percent, some say even 25%, Fe(I) forms !
Still many of these compounds remain a mystery and are worth to be further researched. Iron Chemistry: [Fe(H2O)5NO](2+) an NO (+*-) as Ligand](https://i.ytimg.com/vi/uLh69ukYmrU/mqdefault.jpg)
![Tellurium Chemistry: Aromatic Polycation Te4(2+)
Much like our experiment with Selenium, Tellurium forms polycations in conc. H2SO4 as well. In this case, the color is red. Back then we had an 8-membered crown-shaped ring.
Tellurium, however, forms a different polycation under the same conditions. This time a square is formed which consists of 4 Tellurium atoms. As the system contains 6 pi-electrons* and it is flat we call this a Hueckel aromatic compound.
Besides Te4(2+), S4(2+) and Se4(2+) can form under different conditions as well and those are aromatic, too. Why does this compound form so fast in comparison to a sulfur polycation which requires Oleum to form ? Sulfur is much more electronegative and the cation possesses a much higher acidity. Thus, Tellurium is easier to react it in H2SO4 and no more reactive reagent is required. There are multiple ways to make the Te4(2+) and depending on the method and counterion it can further polymerize forming Te8(4+) as dimer, or [Te4(2+)]x as polymeric chain where the Te-squares are connected via the vertices.
Note:
* If you are unsure how to determine the amount of electrons here, this is the official calculation to this problem:
- Number of valence electrons = 4 x 6 = 24
from this some electrons have to be subtracted
- Number of sigma-electrons = 8
- Amount of lone pairs 2 x 4 = 8
- Charge = 2
If you subtract these 18 from 24 you get 6 pi-electrons in the system. Next to determine aromaticity you can use the Frost-Musulin-diagram. Take the shape of your ring and place it on a vertex. Each vertex is now an energy level. If you take benzene for example you will see that there are two times two vertices on the same height. Those are degenerate energy levels. Each of these layers have to be either completely empty or fully filled to yield a stable compound. Unpaired situations will lead to reactive radicals, which is why there are aromatic, anti-aromatic and non-aromatic compounds and the Hueckel-rules exist.
Ok so we take our square and place it on an edge we get 4 energy levels (where each vertex is). Two of those will be at the same hight and therefore be degenerate. Now we know that we have 6 pi-electrons and each energy level can be filled with two electrons. This will fill the first and the second degenerate layer which is a stable situation making it aromatic. It is also flat, which is a requirement for aromatic compounds as well. Tellurium Chemistry: Aromatic Polycation Te4(2+)](https://i.ytimg.com/vi/uSOnzhbSh6A/mqdefault.jpg)


 (Pd in HCl/H2O2)
Palladium is an interesting element. Being a Platinum-group metal and standing between Nickel and Platinum one might expect it to be unreactive. Funnily this is not the case and some people even joke it could be more reactive than Nickel. Obviously, this might be a bit too much but the reactivity can be compared to the one of silver with one important difference: Palladium usually does not build up many passive layers. Meaning that it can dissolve in HCl for example.
In this video, however, we cheated a little and this is first to make it shorter and second to make it more visible. Usually, oxygen in HCl is enough to slowly dissolve Palladium but we used H2O2 instead of the oxygen here. Now you might say there is no big difference but there is. The redox reaction now changed to the one of an acidified Peroxide which has a huge redox potential being capable of even dissolving gold and platinum to some extent!
And PdCl2 forms Pd(IV) in H2O2 as well!
Note however that we also tried it with HCl and Oxygen and a lot of boiling and it turned yellow as well!
What forms here is the complex [PdCl4](2-). While Nickel(II) already shows some square planar geometry, especially when working with cyano-Ligands for Palladium almost all complexes are square planar.
Also the coordination number of 4 is really common in Palladium chemistry. So if you have to guess, a square planar geometry is always a good guess when dealing with Pd(II). Even the aqua-complex only has 4 Ligands. Palladium Chemistry: [Pd(Cl4](2-) (Pd in HCl/H2O2)](https://i.ytimg.com/vi/wQA5K90Ijqg/mqdefault.jpg)

. If this is acidified, the vanadates can much like the Chromate and Dichromate to Polychromate condense by giving off water and form corner-sharing tetrahedra in long chains. At pH 8 to 13 those shorter Vanadates and the in this experiment used Metavanadates (VO3(-))n form. At pH 2 to 6 the red/orange Decavanadates form and below pH 2 which I am not sure whether we really reached it as we only added some drops to it Vanadyl-cations form [VO2](+) or probably better if you saw our Ammine-copper/nickel video a [VO2(H2O)4](+). This can now be reduced with nascent Hydrogen or Hg:Zn and probably other reducing agents as well to Vanadium(IV) which is blue and looks like this [VO(H2O)5](2+). What is happening is the VO2(+) changes to a VO(2+) and as you see we loose an oxygen in this reaction.
The next step forms the green Vanadium(III) [V(H2O)6](3+) and the purple Vanadium(II) [V(H2O)6](2+). The color green appears in between but seems to be a mixture of the yellow Vanadium(V) and the blue Vanadium(IV).
There is an additional note on the last page in the book which says:
For V(III) its not [V(H2O)6]Cl3 but [VCl2(H2O)4]Cl as trans-Isomer.
For V(II) its not [V(H2O)6]Cl2 but again trans-[VCl2(H2O)4].
V(II) will react with water to form Hydrogen and V(III) again all of them will react with Oxygen to form V(V). Vanadium Chemistry: V(V) reduction to V(IV), V(III) and V(II) using nasc. Hydrogen](https://i.ytimg.com/vi/wbsujp2dEMw/mqdefault.jpg)
 is deprotonated to form [Ni(H2O)4(OH)2] which is often just called Ni(OH)2. If more Ammonia is added the [Ni(NH3)6](2+) complex forms.
Here the color of the Ammine and the Aqua complex differ without any change in geometry or spin which makes this a good example to show how Ligands can cause the color of complexes. If you saw our Vanadium and Manganese reduction you saw how different oxidation states on the central atom change the color as well.
As there are no pi-bonds in water or ammonia there wont be any backbonding-effect so both can be easy compared. Ammonia is a way stronger ligand than water is, which means that the electron density of the electrons donated to the central atom will be closer to the ligand in water than in ammonia which results in a bigger ligand field splitting in the Ammine complex. Light of shorter wavelength must be absorbed now and the complex gets blue shifted from green to purple-blue. As both ligands have only Hydrogen we think the difference comes from the electronegativity. As Oxygen is more electronegative than Nitrogen it will pull the electron density closer to itself causing a red shift in comparison to the Ammonia. Nickel Chemistry: Hexamminenickelchloride](https://i.ytimg.com/vi/wcHXHVu0_TM/mqdefault.jpg)