Carbon dioxide is quite safe and will not kill you if you breathe it. What will kill you is the absence of oxygen: we need to breathe oxygen, because it is necessary to burn the fuel that powers our heart and body, if we breathe only other gases, even if they are harmless, we can die because of absence of oxygen.
Carbon monoxide on the other hand is a deadly poison. It binds to chemicals in the blood, preventing oxygen from being carried by blood to the different parts of the body. This can kill very quickly. It is particularly dangerous because it has no smell.
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