Haemoglobin and Oxygen

Equilibrium
Inês Almeida
January 6, 2022

Abstract
In this article, the transport of oxygen from the lungs to the other cells
of the body by the blood, and the impact of chemical equilibria in these
processes is explored.

1 Introduction
Our bodies are made of cells organized into different organs and tissues,
which perform a variety of functions. All these different body parts need a
particular chemical environment that enables their metabolic reactions and
provides a supply of nutrients and oxygen, and allows for the elimination of
waste products. This ideal environment is provided by the blood. Blood is
an aqueous body fluid, contained in the vascular system and pumped around
the body by the heart. The blood distributes oxygen and nutrients around
the body, carries CO2 generated by the cells to the lungs, and transports
other waste products to the kidneys and liver for processing and elimination.

2 O2 Transport via Metal Complexes

An adult consumes on average 250 ml of oxygen per minute while at rest.
The oxygen is carried in the blood, from the lungs to the tissues where it
is consumed, but only ∼1.5% of it is transported directly dissolved in the
plasma. A much more efficient mechanism is required if all the necessary
oxygen is to be transported to the tissues that demand it the most, and also
allowing it to leave the blood when it reaches those tissues.

2.1 Metal Complexes in the Body

The ability of metal ions to coordinate with and release ligands in some
processes, or to oxidize and reduce in other processes, makes them ideal in
biological systems. The most common metal used in the body is iron, which
also plays a role in the transport of oxygen.
Metal complexes consist of a metal ion, usually a transition metal,
bonded via coordinate covalent bonds (Figure 1) to a small number of an-
ions or neutral molecules called ligands. Ligands with two or more donor

1
Figure 1: Schematic representation of coordinate bonding in metal complexes.

atoms can coordinate to metal ions while simultaneously occupying two or

more coordination sites: these are called polydentate ligands. The number
of occupied coordination sites around the central atom is the coordination
number [1].

2.2 Haemoglobin

Figure 2: Hb molecule model.

Haemoglobin (Hb) is the protein that transports oxygen (O2 ) in the

blood of most vertebrates. In haemoglobin, each subunit contains a heme
group, which can be seen in figure 2 as each subunit is represented in a
different colour and the respective heme group is displayed using the ball-
and-stick representation. Each of these contains an iron atom that is able
to bind to one O2 molecule, which means that one haemoglobin protein can
bind to four oxygen molecules. The heme group is non-planar when it is not
bound to oxygen; this configuration is characteristic of the deoxygenated
heme group, and is usually referred to as a ”domed” shape. When the

2
Figure 3: Schematic representations of the conformational changes upon binding of
oxygen.

Fe in the heme group binds to O2 , the porphyrin ring adopts a planar

configuration and hence the Fe lies in the plane of the porphyrin ring [1].
This is illustrated in Figure 3.

3 Carbon Monoxide Poisoning

O2 binds to haemoglobin in a reversible reaction:

Hb(aq) + 4 O2 (aq) −
↽−
−⇀
− Hb(O2 )4 (aq)
The bonds between CO and haemoglobin are ∼200 times stronger than
the ones between O2 and haemoglobin [2]. This means that the presence
of CO blocks oxygen attachment and lowers the amount of oxygen reaching
the cells. The reaction is:

Hb(aq) + 4 CO(aq) −
↽−
−⇀
− Hb(CO)4 (aq)
Combining the two equations:

Hb(O2 )4 (aq) + 4 CO(aq) −

↽−
−⇀
− Hb(CO)4 (aq) + 4 O2 (aq)
Which is naturally shifted to the right.

3.1 Le Châtelier’s Principle

Treatment involves giving the patient pure oxygen to reverse the condition.
Le Châtelier’s Principle states that ”if a system at equilibrium for a
long period of time is subjected to a change in concentration, temperature,
volume, or pressure, the system readjusts to partially counter the applied
change, which results in a new equilibrium”.
By increasing the concentration of O2 , the system will shift to the left
to reduce the concentration of O2 , increasing the concentration of Hb(O2 )4 .

Tasks
1. Highlight/google words you do not understand.
2. Think about questions you might have.

3
Questions
1. What characteristics do transition metals have that make them prone
to forming complex ions?
2. Why does the shape of the heme group change upon the binding of
oxygen?
3. Look at the equilibrium reaction for O2 and Hb. How can you explain
the binding of oxygen in the lungs and release of oxygen in the cells?
4. Consider the fact that the Hb binds more strongly to ligands such as
CO or CN− than O2 . The magnitude of this difference, as well as
affinity between Hb and O2 varies across species. Discuss if it would
be beneficial for humans if the O2 affinity were greater.
5. Discuss how the problem of CO poisoning can be approached through
the calculation of the equilibrium constant, Keq
6. Hyperbaric chambers have pressures of ∼ 2.5-3 atm. Why are hyper-
baric chambers frequently used to treat CO poisoning?

4 References
[1] R. Casiday and R. Frey, “Hemoglobin and the heme group: Metal com-
plexes in the blood for oxygen transport,” Sep 2008.
[2] R. B. Cope, “Chapter 24 - carbon monoxide: can’t see, can’t smell,
body looks red but they are dead,” in Handbook of Toxicology of Chem-
ical Warfare Agents (Third Edition) (R. C. Gupta, ed.), pp. 353–371,
Boston: Academic Press, third edition ed., 2020.